Ligand exchange thermochromic, (letc), systems

ABSTRACT

Ligand exchange of thermochromic, LETC, systems exhibiting a reversible change in absorbance of electromagnetic radiation as the temperature of the system is reversibly changed are described. The described LETC systems include one or more than one transition metal ion, which experiences thermally induced changes in the nature of the complexation or coordination around the transition metal ion(s) and, thereby, the system changes its ability to absorb electromagnetic radiation as the temperature changes.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application Ser.No. 60/841,827 filed on Sep. 1, 2006, the contents of which are herebyincorporated by reference.

DEFINITION OF TERMS/ABBREVIATIONS

-   (4-MeOPh)₂PO₂ ⁻=bis(4-methoxyphenyl)phosphinate-   18-crown-6=1,4,7,10,13,16-hexaoxacyclooctadecane-   1-EtBIMZ=1-ethyl-1H-benzimidazole-   1-MeBIMZ=1-methyl-1H-benzimidazole-   4-(3-PhPr)Pyr=4-(3-phenylpropyl)pyridine)-   acac=acetylacetonate-   BIMZ=benzimidazole-   Bu₃PO=tributylphosphine oxide-   CF₃COOLi=lithium trifluoroacetate-   Di-TMOLP=di-trimethylolpropane-   DMSO=dimethylsulphoxide-   DP=dipyridyl=2,2′-bipyridine-   EG=ethylene glycol-   EXM=Exchange Metal

HεL=high molar absorption coefficient ligand=high epsilon ligand

-   HεMLC=high molar absorption coefficient MLC=high epsilon MLC-   LETC=ligand exchange thermochromic(s)-   LεL=low molar absorption coefficient ligand=low epsilon ligand-   LεMLC=low molar absorption coefficient MLC=low epsilon MLC-   m=molal=moles of solute per kilogram of solvent-   M=molar=moles of solute per liter of solution-   Me=metal ion-   MLC=metal-ligand complex-   N-Bu-di(1-MeBIMZ-2-yl-methyl)amine=N,N-bis[(1-methyl-1H-benzimidazol-2-yl)methyl]butanamine-   NIR=near infrared-   nm=nanometer-   NPG=neopentyl glycol=2,2-dimethylpropane-1,3-diol-   N—Pr-dipicolylamine=N,N-bis(pyridine-2-ylmethyl)propan-1-amine-   N—Pr-DPamine=N-propyl-N-pyridin-2-ylpyridin-2-amine-   Ph₃P═PPh₃=triphenylphosphine-   PVB=poly(vinyl butyral)-   R/O=Ring Opening TC Compound-   SRT™=sunlight responsive thermochromic-   TBABr=tetrabutylammonium bromide-   TBACl=tetrabutylammonium chloride-   TBAI=tetrabutylammonium iodide-   TC=thermochromic(s)-   TEACl.H₂O=tetraethylammonium chloride monohydrate-   TMEDA=N,N,N′,N′-tetramethylethylenediamine-   TMOLP=trimethylolpropane=2-ethyl-2-(hydroxymethyl)propane-1,3-diol-   TTCTD=1,4,8,11-tetrathiacyclotetradecane-   UV=ultraviolet-   Y=% white light transmission based on 2° exposure of a D₆₅ light    source-   ε=molar absorption coefficient=molar absorptivity, in    liters/(mole*cm)-   γ-BL=gamma-butyrolactone-   λ=wavelength in nanometers

BACKGROUND

Many chromogenic phenomena are known in which a change in color or achange in light absorption results from some action or stimulus exertedon a system. The most common chromogenic phenomena are electrochromics,(EC), photochromics, (PC), and thermochromics, (TC). Many phenomena arealso known in which optical changes, like light scattering or diffusereflection changes, take place as a result of some action or stimulusexerted on a system. Unfortunately, referring to these as chromicphenomena has led to a fair amount of confusion in the past. We preferto distinguish light scattering systems from chromogenic systems byreferring to the light scattering phenomena as a phototropic,thermotropic or electrotropic phenomena. This distinction and otherdistictions are elaborated on below.

In general, and especially for the sake of the patent application, theterms used for an optical phenomena, should relate to the direct,primary action causing the phenomena. For example, modern dayelectrochromic systems generally involve electrochemical oxidation andreduction reactions. Thus an electrical process directly causesmaterials to change their light absorbing or light reflectingproperties. Alternatively, electrical energy can also be used togenerate heat or light and this heat or light, in turn, may be used toaffect a thermochromic or a photochromic change. However, the indirectuse of electricity should not make these electrochromic phenomena. Forexample, a thermochromic layer may increase in temperature and lightabsorption when in contact with a transparent conductive layer which isresistively heated by passing electricity through the transparentconductive layer. However, in accordance with the terminology usedherein, this is still a thermochromic device and should not be called anelectrochromic device. Also, just because an electric light produced UVradiation that caused a color change by a phototchemical reaction, likethe ring opening of a spirooxazine compound, that would not make such aprocedure a demonstration of electrochromics.

A similar distinction should be made with a thermochromic layer that isresponsive to sunlight as described in U.S. Pat. Nos. 6,084,702 and6,446,402. The thermochromic layer may be heated by absorbing sunlightor being in contact with another layer that absorbs sunlight. Heresunlight exposure changes the color and/or the amount of light absorbedby the thermochromic layer. However, this is still a thermochromicphenomenon because a heat induced temperature change causes thechromogenic change and the same change takes place when the layer isheated by other means. The absorbed photons from the sun are onlyconverted to heat and do not directly cause a photochromic change.Accordingly, the term photochromics should be reserved for systems inwhich the absorption of a photon directly causes a photochemical orphotophysical reaction which gives a change in color or a change in thesystem's ability to absorb other photons.

In addition to chromogenic systems, there are a variety of systems withreversible changes in light scattering. The more widely studied lightscattering systems include: (1) lower critical solution temperature,LCST, polymeric systems; (2) polymer dispersed liquid crystal, PDLC,systems; (3) polymer stabilizer cholesteric texture, PSCT, systems and(4) thermoscattering, TS, systems. Additional description of these andother light scattering phenomena may be found in U.S. Pat. No.6,362,303. In the past, several of these phenomena have been calledthermochromic and even electrochromic. From our standpoint thesephenomena are neither thermochromic nor electrochromic since the wordchroma relates to color and the intensity and quality of color. Theseare better termed thermotropic or electrotropic to help indicate thechange in state that takes place.

Definitions rarely cover every eventuality, especially when it comes toborderline cases. Hence electrochemical systems that change fromcolorless and non-light scattering to specularly reflecting are stillgenerally termed electrochromic because of the electrochemical nature ofthese processes. Also, some thermochromic systems involve changesbetween liquid and solid phases and could conceivably be calledthermotropic systems. But these systems have dramatic changes in lightabsorption and are still termed thermochromic. On the other side, somereversible light scattering systems may have some spectral selectivityto the light scattering and hence give rise to some color appearance.Yet the primary change is between light scattering and non-lightscattering states. Even the change in some systems from colorless andnon-light scattering to a frosted, diffusely reflecting and whiteappearance might suggest a color change to the color white. However, westill term these tropic and not chromic changes.

In summary, systems without any substantial change in light scattering,that primarily involve a change in color, intensity of color orabsorption of light, as well as those electrochemical and thermochemicalphenomena that give a change in specular reflectance, are hereinunderstood to be chromic or chromogenic phenomena. One of these chromicphenomena—thermochromics, as defined herein, is the subject of thepresent invention.

Many thermochromic materials and phenomena are known. These includereversible and irreversible changes in optical character. A well knownthermochromic phenomena, for use with windows, involves metal oxide thinfilms. Most notably films of VO₂, and doped versions thereof, are knownto reversibly change their specular reflectance in the NIR with changesin temperature. Thermochromic processes with changes in light absorptionare observed when heating causes: (1) an increase in the amount of ringopening of certain spiro compounds; (2) the dissociation of certainanions from certain triarylmethane dyes or (3) the dissociation ofcertain “dimeric” substances into highly absorbing “monomeric” freeradicals. Thermochromic phenomena are also involved in phase changesystems which change from highly absorbing to colorless or nearlycolorless when certain pH indicators change their association withcertain weak acids during a melting or solidification process.

Still other reversible thermochromic systems involve thermally inducedchanges in the way ligands associate with transition metal ions. Thepresent application discloses particularly useful versions of thesemetal-ligand thermochromic systems and combinations of these systemswith other thermochromic systems.

SUMMARY OF THE INVENTION

In accordance with the one aspect of the present invention, athermochromic system is disclosed comprising Ni(II), a first ligand,which forms a LεMLC with Ni(II) and a second ligand, which forms a HεMLCwith Ni(II) in a polymer wherein the system is in the form of a solid orsemi-solid layer and the system exhibits a reversible net increase inlight energy absorbance in the 400 nm to 1400 nm range as thetemperature of the system is increased. The polymer may function as theligand which forms a LεMLC.

In accordance with another aspect of the present invention, athermochromic system is disclosed comprising Co(II) and first and secondligands wherein the system exhibits a reversible increase in its abilityto absorb light energy in the 400 nm to 1400 nm range as the temperatureof the system is increased.

In accordance with yet another aspect of the present invention, athermochromic system is disclosed comprising a polymer layer containinga transition metal ion, a ligand capable of forming a HεMLC with thetransition metal ion and a second ligand such as a polymer, diol ortriol.

The thermochromic systems of the present application are, herein,termed: ligand exchange thermochromic, LETC, systems. LETC systems havethermochromic activity which results in a reversible change inabsorbance of electromagnetic radiation as the temperature of the systemis reversibly changed. That the change is reversible means that theamount of change in absorbance remains fairly consistent, for both theincrease and decrease in absorbance throughout a given temperaturerange, on repeated temperature cycling, for some useful number ofcycles. The thermochromic systems of this invention have a reversible,net increase in their ability to absorb light energy in the visibleand/or NIR range as the temperature of the system is increased and a netdecrease in their ability to absorb light energy in the visible and/orNIR range as the temperature of the system decreases for temperatureswithin the active range of the system. The active temperature range ofthe system is determined by the thermodynamic properties of the LETCreactions. For many of our applications the active temperature rangeincludes 0 to 100 degrees Celsius.

LETC systems comprise one or more than one transition metal ion, whichexperiences thermally induced changes in the nature of the complexationor coordination around the transition metal ion(s) and thereby thesystem changes its ability to absorb electromagnetic radiation as thetemperature changes.

In accordance with particularly useful systems described herein, theelectromagnetic radiation, for which absorbance changes occur, is in thevisible and NIR portions of the electromagnetic spectrum. Some of thesystems described herein also exhibit changes in absorbance in theultraviolet. The change in light absorption on heating of the LETCsystems generally results in a change from one color to another colorand/or a darkening of the color of the system. However, if the increasein light absorption is predominantly in the NIR, the LETC system maystill be very useful even though little or no visual color changeoccurs.

The term visible light generally applies to that portion of theelectromagnetic spectrum sensed by the human eye. While some definitionsmight limit the terms “light” and/or “photon” to the visible portion ofa spectrum produced by a source of electromagnetic radiation, for thepurposes of this patent application, the terms “light” and “photon” alsoapply to the near ultraviolet and near infrared portions of the spectra,incident on the earth's surface, from sources of electromagneticradiation like the sun. The wavelengths of ultraviolet light of interestare from about 280 nanometers to about 400 nanometers. The wavelengthsof the visible light of interest are from about 400 nanometers to about700 nanometers. The wavelengths of NIR light of interest for our LETCsystems are from about 700 nanometers to about 1400 nanometers. Thus thevisible through NIR range wherein reversible net light energy absorbanceincreases are of interest is from about 400 nm to about 1400 nm.

The energy of each photon is inversely proportional to its wavelengthand is determined by Planck's constant multiplied by the frequency ofthat photon. As a LETC system is heated, at least one light absorbingspecies decreases in concentration thereby decreasing the system'sability to absorb photons related to its absorption spectra. At the sametime, at least one light absorbing species increases in concentrationthereby increasing the system's ability to absorb photons related to itsabsorption spectra. The ratio of the amount of energy absorbed to theamount incident on the system depends on several factors including (1)the absorption spectra of the LETC system at a given temperature; (2)the intensity and spectral distribution of the light source and (3) theexposure time.

For certain LETC systems disclosed and for the particular applicationsthereof, as the temperature of the LETC system increases there is anincrease in the ratio of [the total energy per unit time of all visibleand NIR electromagnetic radiation, (photons), absorbed by the system] to[the total energy per unit time of all visible and NIR electromagneticradiation, (photons), incident on the system] from a broad band sourceof electromagnetic radiation incident on the system. For particularlyuseful applications of the LETC systems or layers disclosed herein,there is a net increase in the ability of the system to absorb incidentvisible and NIR sunlight power, (or energy over time), as thetemperature of the system increases. In most cases, this means that theLETC systems become darker in color as the temperature of the systemsincrease.

The LETC systems may be liquid solutions, solid polymer layers, orsemi-solid polymer layers, physical gels or chemical gels.

The present application discloses LETC systems, ligands, particularlyuseful compositions and combinations of LETC systems.

The present application describes high performance TC systems based oniron, cobalt, nickel and copper ions with a variety of ligands.

The present application describes LETC systems with advantageous ratiosof ligand to metal ion concentrations and particularly useful systemswith respect to the choice of solvent and/or polymer matrix.

The present application discloses high performance TC systems incombination with a seal which minimizes the ingress of oxygen.

LETC systems by themselves and in combination with other thermochromicsystems and compositions are disclosed.

Also described herein are processes for producing thermochromic layersand novel structures for the use of LETC systems in variousapplications.

Described herein are applications of LETC systems in variable lighttransmission windows for residential and commercial buildings includingskylights and atrium glazing and variable light absorption windows forboats, ships, aircraft and motor vehicles including moon roofs and sunroofs. The windows may include artful designs of different colored LETCsystems like a variable light transmission stained glass window.

The systems disclosed herein are particularly useful in providing thethermochromic activity in the inventions disclosed in U.S. Pat. Nos.6,084,702 and 6,446,402, the contents of which are hereby incorporatedby reference.

TC Systems and MLC Systems

Thermochromic systems that involve reversible changes in the associationof ligands with transition metals have been described previously. Manyof these, along with other types of inorganic thermochromic materials,are described in “Inorganic Thermochromism” by K. Sone and Y. Fukuda,Springer-Verlag (1987) and the references therein.

Other literature that describes thermochromics involving transitionmetal ions is found in:

-   Jesse Day, “Chromogenic Materials, Electrochromic and Thermochromic”    in Kirk-Othmer Encyclopedia of Chemical Technology 3^(rd) Edition    Volume 6, pp 129-142, John Wiley and Sons (1979).-   Charles Greenberg, “Chromogenic Materials (Thermochromic)”    Kirk-Othmer Encyclopedia of Chemical Technology 4^(th) Edition    Volume 6, pp 337-343, John Wiley and Sons.-   “Thermochromism of Inorganic Compounds”, J. H. Day, Chemical Reviews    68, 649-657 (1968)

There is extensive literature on MLC's apart from TC technology; see forexample:

-   “Inorganic Electronic Spectroscopy” by A. B. P. Lever, Elsevier    Publishing Co. (1968) and (1984).-   “Comprehensive Coordination Chemistry: Synthesis, Reactions,    Properties & Applications of Coordination Compounds” Editors R. D.    Gillard and G. Wilkinson, Elsevier Ltd. (1987)-   “Comprehensive Coordination Chemistry II From Biology to    Nanotechnology”, Editors J. A. McClevety and T. A Meyer, Elsevier    Ltd. (2004)

BRIEF DESCRIPTION OF FIGURES

FIG. 1-46 are absorption spectra for the systems described in Examples1-46, respectively;

FIG. 47 is a plot of K_(eq) (85 C) to K_(eq) (25 C) as a function ofΔH°;

FIG. 48 shows the influence of ΔS° on Absorbance and Temperature;

FIG. 49 shows the temperature dependence of Absorbance for variousratios of [HεL_(T)]/[M_(T)];

FIG. 50 is a plot of Transmission of SRT™ vertically positioned windowsbased on time of day and direction;

FIG. 51-57 are absorption spectra for the systems described in Examples279-285, respectively; and

FIG. 58 is the spectral data for Example 294.

DETAILED DESCRIPTION

The term “substituted” as in “substituted alkyl” and the like, meansthat in the group in question, at least one hydrogen atom bound to acarbon atom is replaced with one or more substituent groups, such ashydroxy, alkoxy, alkylthio, phosphino, amino, halo, silyl, and the like.When the term “substituted” introduces a list of possible substitutedgroups, it is intended that the terms apply to every member of thatgroup.

The term “alkyl” as used herein refers to a branched or unbranchedsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 20 carbon atoms, more particularly containing 1 toabout 6 carbon atoms. The term “aryl” as used herein refers to a groupcontaining an aromatic ring. Aryl groups herein include groupscontaining a single aromatic ring or multiple aromatic rings that arefused together, linked covalently, or linked to a common group such as amethylene or ethylene moiety. In particular embodiments, arylsubstitutents include 6 to about 50 atoms other than hydrogen, typically6 to about 20 atoms other than hydrogen. Furthermore, the term “aralkyl”refers to an alkyl group substituted with an aryl group typicallycontaining from 7 to 20 carbon atoms.

The terms “heterocycle” and “heterocyclic” refer to a cyclic group,including ring-fused systems, including heteroaryl groups as definedbelow, in which one or more carbon atoms in a ring is replaced with aheteroatom—that is, an atom other than carbon, such as nitrogen, oxygen,sulfur, phosphorus, boron or silicon. Heterocycles and heterocyclicgroups include saturated and unsaturated moieties, including heteroarylgroups as defined below. The term “heteroaryl” refers to an aryl groupthat includes one or more heteroatoms in the aromatic ring.

LETC activity is observed when a temperature change causes theassociation of ligands with transition metal ions to change or exchangein such a way that a variation in the UV, visible and/or the NIR lightabsorption of the system occurs giving a reversible net increase in thesystem's ability to absorb visible and/or NIR light energy as thetemperature is increased. A LETC system includes, at least, one type oftransition metal ion and at least two types of ligands. Unless theligands function as the entire solvent, the system also includes someother type of solvent for the transition metal ion and the ligands sothat they are together in a liquid or a solid solution.

The solvent may be an aqueous, nonaqueous or ionic liquid; aplasticizer; a polymer; some additive(s) dissolved in a polymer; thematrix portion or phase of an organic, inorganic or hybrid gel; theliquid portion or phase of a gel; or some combination of these acting asco-solvents. The solution may be a free flowing or a viscous liquid, anon free flowing or thixotropic gel, or a solid or a semi-solid polymer.All of these solvents provide enough mobility for the ligands totransfer in and out of coordination with transition metal ions.

The present application describes various LETC systems in whichremarkable amounts of transition metal salts, ligand salts, non-ionicligands and other key additives are all dissolved at the same time insolid polymer layers and remain in solution over the temperature rangeof interest of use. Not only can such solutions be prepared, but selectsystems have been discovered that neither form precipitates nor do thelayers develop haze over prolonged periods at elevated temperatures,during numerous temperature cycles or during extensive exposure tosunlight or simulated sunlight.

In the LETC systems of interest, transition metal ions in solution areeither solvated, complexed, coordinated or ligated by ions and/ormolecules. The ions and/or molecules in the primary coordination sphereof the metal ion are often referred to as ligands. For the purpose ofthe present application, any ion or molecule that either solvates,complexes, coordinates, ligates or directly interacts with a metal ion,in such a way that it impacts the light absorption character of thesystem, is referred to as a ligand. Also any transition metal ion insolution is considered to be in a complex or coordination compound evenif the coordinating power of the solvent or other ligands is relativelyweak. Typically, the transition metal is in the form of a cation.

When a transition metal ion is surrounded by certain ligands, a“metal-ligand complex”, (MLC), may be formed which has low molarabsorptivity throughout the visible and NIR range. This MLC is, herein,referred to as a “low ε MLC”, (LεMLC). When the same transition metalion is surrounded by other ligands, a MLC may be formed which has ahigher level of molar absorptivity somewhere in the visible and NIRspectral region. This MLC is, herein, referred to as a “high ε MLC”,(HεMLC). The LεMLC and the HεMLC may absorb at the same or some of thesame wavelengths or at substantially different wavelengths. Both theLεMLC and the HεMLC generally absorb fairly strongly in the UV, andwhile changes in the amount and the wavelengths of UV light absorbed maybe useful aspects of the LETC process the primary applications involvechanges in the visible and NIR absorption ability. The ε in thesedesignations refers to the molar absorption coefficient or molarabsorptivity of the MLC in solution. The units of liters/(mole*cm) areused for ε. HεMLC's have an ε of greater than or equal to 50liters/(mole*cm) at some or at least one wavelength between 400 nm and1400 nm. LεMLC's have an ε of less than 50 liters/(mole*cm) for allwavelengths between 400 nm and 1400 nm.

Any ligand in a LεMLC is, herein, referred to as a low ε ligand, LεL.Any ligand in a HεMLC is, herein, referred to as a high εligand, HεL.When a ligand is not coordinated to a transition metal in a LεMLC or aHεMLC, the determination of whether or not the ligand is a LεL or HεL isnot so clear sometimes. Thus for the sake of the present disclosure, thedetermination of ligand type is made by the side on which the ligandappears in the main or predominant equilibrium reaction equation of theLETC system. A ligand, not coordinated to a metal ion, that appears onthe same side of an equilibrium equation as the LεMLC(s) is a HεL. Aligand, not coordinated to a metal ion, that appears on the same side ofan equilibrium equation as the HεMLC(s) is a LεL. This is illustrated bythe following equation:LεMLC+yHεL

HεMLC+xLεL  (1)wherein x and y are numeric variables that designate the number of LεLand HεL, respectively. While most ligands are predominately used as aHεL or predominately used as a LεL, there are exceptions which will beillustrated in the section below on “LETC Reaction Equilibria” and inTable 27.

We understand that a LETC process occurs, as the temperature is raised,because a decrease in LεMLC concentration and an increase in HεMLCconcentration takes place by a change in association of the ligands withthe transition metal ion(s) in the MLC(s). Thus, an increase intemperature causes the number of transition metal ions in LεMLC(s) todecrease and the number of transition metal ions in HεMLC(s) toincrease. This results in a decrease in absorption at the wavelengthsabsorbed by the LεMLC and an increase in absorption at wavelengthsabsorbed by the HεMLC. For the LETC systems described herein, the resultof these MLC transformations is a reversible, net increase in thesystem's ability to absorb sunlight energy as the temperature isincreased.

Some thermochromic systems in the literature are based on the reversibleloss and gain of water by a thermochromic layer. However, in accordancewith certain aspects of the present invention, unless otherwisespecified, the water content of the LETC systems of the presentinvention is kept as low as is reasonably possible. Also, whether or notwater is present, it is believed that the LETC processes describedherein occur just because of the rearrangements in the way ions andmolecules associate and not due to materials lost from or gained by thesystem. Thus, in accordance with certain aspects of the presentinvention, all of the active ingredients in the TC system remain in thesame solution or layer throughout the operation or use of the system.

For discussions of thermodynamics, molar absorption coefficients, etc.it is convenient to use concentrations in molarity. For molarity we usethe definition: “moles of solute per liter of solution” and designatemolarity with the symbol, “M”. However, for making up practicalformulations it is often convenient to use molality. The molality isindependent of temperature whereas molarity is affected by the thermalexpansion of the solution. For molality we use the definition: “moles ofsolute per kilogram of solvent” and designate molality with the symbol,“m”. If concentration is reported in molality, the value for thisconcentration in molarity for this solution may be determined bymeasuring the total volume of the solution after it is prepared.

The components of a LETC system include one or more than one type oftransition metal ion, one or more than one type of LεL, one or more thanone type of HεL and a solvent which provides the medium for the exchangeprocess. The solvent itself may act as a LεL or HεL. Alternatively, theLεL's and/or the HεL's may be a part of the solvent system that helpssolubulize other constituents.

Transition Metal Ions

Described herein are many particularly useful LETC systems based oncomplexes with first row transition metals ions. LETC systems comprisingFe(II), Co(II), Ni(II) and/or Cu(II) ions are disclosed herein. In LETCsystems, the transition metal ions are considered electron acceptors.This means that the transition metal ions associate with electron donorsin the sense that Lewis acids associate with Lewis bases. This isdistinguished from the situation of complete electron transfer to anacceptor in which the acceptor is reduced.

Useful transition metal ion concentrations depend on (1) the desiredlevels of absorbance and absorbance change, (2) the path length, (layerthickness), of the LETC system, (3) the ε of the LεMLC and (4) the ε ofthe HεMLC. If the ε of the LεMLC is sufficiently low that its absorbancecan be ignored, and A(T_(H), λ) is the desired absorbance at a highertemperature of operation, (T_(H)), at a particular λ, then the metal ionconcentration, (in moles per liter), must be equal to or greater thanA(T_(H), λ)/(ε(HεMLC, λ)*b). Where b is the path length or layerthickness in centimeters and ε(HεMLC, λ) is the molar absorptioncoefficient of the HεMLC in liter/(mole*cm) at ε. For example, if anA(T_(H), λ)=1 is desired at an elevated temperature, the ε of the HεMLCis 250 liters/(mole*cm) at λ and the desired layer thickness is 0.05 cm,then the minimum transition metal ion concentration would be 0.08M, forthe unlikely event that all the transition metal ion could be shiftedinto the HεMLC. In practice the transition metal ion concentration wouldhave to be higher than 0.08M and preferably would be greater than orequal to 1.5 times the minimum.

Generally, if the ε of the LεMLC is not too high and a thin TC layer isdesired, (as it normally is), then metal ion concentration is made ashigh as possible while still leaving opportunity to provide enough HεLto give a ratio of [HεL_(T)]/[Me_(T)] greater than 4, where the bracketsare used to designate concentration and the subscript T designates thetotal concentration, in any form in the system, in moles per liter. Thus[HεL_(T)] and [Me_(T)] are the total concentrations of various types ofHεL's and various types of Me in the system that could potentiallyparticipate in HεMLC's. The upper limit of transition metal ionconcentration is determined to some extent by the solubility limit ofthe transition metal ions in the system, but more often by thesolubility limit of the HεL and/or the LεL in the system. For mostapplications it is desirable that the system remain free of precipitatesand haze at all temperatures of use, throughout the useful life of thethermochromic system.

Sources of transition metal ions include: hydrated and anhydrous saltsof first row transition metal ions. Other sources are anhydrouscomplexes and complexes in which the transition metal has a coordinationnumber of four or six in the complex. Particularly useful anions for thetransition metal salts and complexes are halides, carboxylates, nitrate,perchlorate, tetrafluoroborate, phosphinates, hexafluorophosphate,hexafluoroarsenate, trifluoromethanesulfonate,bis(trifluoromethane)sulfonamide, tosylates and tetraarylborates.

Sources of transition metal ions include but are not limited to:chromium(III) chloride hexahydrate, cobalt(II) bromide, cobalt(II)chloride, cobalt(II) chloride hexahydrate, cobalt(II) iodide, cobalt(II)nitrate hexahydrate, cobalt(II) tetrafluoroborate hexahydrate,copper(II) acetate monohydrate, copper(II) bromide, copper(II) bromidedihydrate, copper(II) chloride, copper(II) chloride dihydrate,copper(II) nitrate hemipentahydrate, copper(II) perchlorate hexahydrate,copper(II) trifluoroacetate hydrate, iron(II) bromide, iron(II)tetrafluoroborate, manganese(II) bromide, manganese(II) nitratehexahydrate, nickel(II) bis(diisobutyldithiophosphinate), nickel(II)bromide hexahydrate, nickel(II) carbonate hexahydrate, nickel(II)chloride hydrate, nickel(II) cyclohexanebutyrate, nickel(II) iodide,nickel(II) iodide hexahydrate, nickel(II) nitrate hexahydrate,nickel(II) perchlorate hexahydrate, nickel(II) tetrafluoroboratehexahydrate

Particularly useful sources of transition metal ions that are complexesinclude without limitation:

-   bis(1-ethyl-1H-benzimidazole)diiodonickel(II);-   bis(acetylacetonato)nickel(II);-   copper    bis(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate);-   copper(II) hexafluoroacetylacetonate hydrate;-   dibromo(1′-ethyl-1-methyl-1H,1′H-2,4′-bibenzimidazole)nickel(II);-   dibromo[2,2′-propane-2,2-diylbis(1-pentyl-1H-benzimidazole)]nickel(II);-   dibromo{6-methyl-N-[(6-methylpyridin-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine}nickel(II);-   dibromo[N-butyl-1-ethyl-N-(1-ethyl-1H-benzimidazol-2-yl)-1H-benzimidazol-2-amine]nickel(II);-   dibromo(N-butyl-N-pyridin-2-ylpyridin-2-amine)nickel(II);-   dibromo(N-pyridin-2-ylpyridin-2-amine)nickel(II);-   dibromobis[1-(3-phenylpropyl)-1H-imidazole]nickel(II);-   dibromobis(1-ethyl-1H-benzimidazole)nickel(II);-   dibromobis(1-pentyl-1H-benzimidazole)nickel(II);-   dibromobis(2,2-dimethylpropane-1,3-diol)nickel(II);-   dibromobis[2-ethyl-2-(hydroxymethyl)propane-1,3-diol]nickel(II);-   dibromobis(triphenylphosphine)nickel(II);-   dibromotris(2,2-dimethylpropane-1,3-diol)nickel(II);-   diiodobis[1-(3-phenylpropyl)-1H-imidazole]nickel(II);-   diiodobis[2-ethyl-2-(hydroxymethyl)propane-1,3-diol]nickel(II);-   diiodobis(tricyclohexylphosphine)nickel(II);-   diiodobis(triphenylphosphine)cobalt(II);-   diiodobis(triphenylphosphine)nickel(II);-   lithium tetrabromonickelate(II);-   nickel(II) bromide-(2-methoxyethyl ether complex);-   nickel(II) bromide-(ethylene glycol dimethyl ether complex);-   tetrabutylammonium tetrabromonickelate(II);-   tetrabutylammonium tetrachloronickelate(II);-   tetrabutylammonium tetraiodonickelate(II);-   tetraethylammonium tetrabromocobaltate(II);-   tetraethylammonium tetrabromonickelate(II);-   tetrabutylammonium triiodo[4-(3-phenylpropyl)pyridine]nickelate(II);    and-   tetrabutylammonium triiodo(triphenylphosphine)nickelate(II).

The use of metal complexes can be advantageous because just the act ofpreparing complexes often improves the purity of these sources oftransition metal ions. Many simple transition metal salts contain tracesof hydroxides, oxides and oxyhydroxides that cause haziness inthermochromic systems prepared from these salts. Complex formation oftenlargely eliminates or avoids these impurities. Also, many of thenon-ligating impurities which might be present in a batch of ligandmaterial are often excluded when the complex is formed in the process ofsynthesizing the complex. Thus ligands added as part of a complex areoften more pure than ligands added directly to the rest of the system.While complexes, once prepared, may be further purified, surprisingly wehave discovered that just preparing the complexes often eliminates manyof the impurity issues that might otherwise detract from preparingstable, high performance thermochromic systems. In addition, thesecomplexes are often less hygroscopic than most simple metal salts whichassists in preparing systems with low water content. Even complexes thatare hygroscopic are often less prone to forming hydroxides, oxides andoxyhydroxides during storage as compared to metal salts like e.g. simplehalide salts. Significant advantages are also realized with the use ofcomplexes since these complexes are usually more readily dispersed anddissolved in polymers in the LETC layer production process. Thisfacilitates the production of uniform composition and uniformperformance layers especially in the extrusion processes preferred formaking LETC layers.

Types of Ligands in LETC Systems

In LETC systems, the ligands serve as electron donors. This means thatthe ligands associate with transition metals in the sense that Lewisbases associate with Lewis acids. This is distinguished from thesituation of complete electron transfer from a donor in which the donoris oxidized. A definition for HεL's and LεL's is given above. However, amolecule or ion may be a HεL under one set of conditions and a LεL underanother set of conditions, and of course vice versa. Thus one must lookat the main or predominant equilibrium reaction equation of a LETCsystem to see if the ligand is a LεL or a HεL.

A given ligand may coordinate to a metal ion at one or more than onesite around the metal ion. Ligands that coordinate in a single site arereferred to as monodentate and ligands that coordinate in multiple sitesare referred to as polydentate. As the names signify, bidentate,tridentate, tetradentate and hexadentate ligands coordinate in two,three, four and six sites, respectively.

Metal ions may be coordinated by ligands of a single type like many wellknown hexa-aquo coordinated ions in which six water molecules surround ametal ion or when four of a single type of halide anions surround ametal ion as in a tetrahalo-metalate complex. These are known ashomoleptic complexes. However, many heteroleptic, (mixed ligand),complexes are known where two or more different ligand types coordinateto the same metal ion at the same time. For example, a heterolepticcomplex is formed when the ligands around a single metal ion consist oftwo iodide ions and two molecules of some type of phosphine compoundwhich coordinates to metal ions through phosphorus. This is illustratedfor increases in concentration with increasing temperature forCo(II)I₂(Ph₃P)₂ in FIG. 9 and for Ni(II)I₂(Ph₃P)₂ in FIG. 27. Anotherexample is iodide ions and trifluoroacetate ions coordinated at the sametime to Co(II) ions as shown in FIG. 4. Many other TC systems thatinvolve heteroleptic HεMLC's are listed in Table 27.

LεL

The best LεL's promote the formation of LεMLC's with the least amount ofabsorbance, (lowest ε's), and help promote the highest positive valuesof ΔH° and ΔS° for the LETC reaction, (as discussed later). They alsohelp solubilize other system components and help provide desirablephysical properties to TC layers when the layer involves a polymericmaterial which comprises the rest of the TC system.

Hydroxyl groups attached to carbon provide LεL functionality. The MLC's,formed by coordination of ligands to transition metals through hydroxylgroups, tend to have some of the lowest values for throughout thevisible light wavelength range. In general, the useful LεL's for LETCsystems include water, diols, triols or polyols. Water is a useful LεLor co-LεL when Fe(II) and/or Cu(II) ions are used in the LETC system.While water is a useful LεL with regard to good thermochromicperformance with other transition metal ions, it is to be avoided orlimited to low concentrations in most LETC systems because of itsrelatively low boiling point and its reactive nature.

Some diols that are useful as LεL's are represented by the followingstructure:

wherein R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected fromstraight, branched, substituted or unsubstituted alkyl; substituted orunsubstituted aryl; or substituted or unsubstituted aralkyl. Somespecific examples of the above structure are: 1,3-Cyclohexanediol;1,1-Bis(hydroxymethyl)cyclopropane; 2,2-Bis(hydroxymethyl)propionicacid; 2,2-Dibutyl-1,3-propanediol; 2,2-Diethyl-1,3-propanediol;2,2,4-Trimethyl-1,3-pentanediol; 2,4-Dimethyl-2,4-pentanediol;2,4-Pentanediol; 2-Bromo-2-nitro-1,3-propanediol; Serinol;2-Butyl-2-Ethyl-1,3-propanediol; 2-Ethyl-1,3-hexanediol;2-Methyl-1,3-propanediol; 2-Methyl-2,4-pentanediol;2-Methyl-2-propyl-1,3-propanediol; 2-Methylenepropane-1,3-diol;2-Phenyl-1,3-propanediol; Cyclohex-3-ene-1,1-diyldimethanol;3-Methyl-1,3-butanediol; 3-Methyl-2,4-heptanediol;[2-(2-phenylethyl)-1,3-dioxane-5,5-diyl]dimethanol; Neopentyl Glycol;and Trimethylolpropane allyl ether.

Some triols that are useful as LεL's are represented by the followingstructure:

wherein R is selected from straight, branched, substituted orunsubstituted alkyl; substituted or unsubstituted aryl; substituted orunsubstituted aralkyl; a nitro group; or a substituted or unsubstitutedamino group. Some specific examples of the above structure are:2,2′-(propane-1,3-diyldiimino)bis[2-(hydroxymethyl)propane-1,3-diol];2-[bis(2-hydroxyethyl)amino]-2-(hydroxymethyl)propane-1,3-diol;Dipentaerythritol; Pentaerythritol;2-(bromomethyl)-2-(hydroxymethyl)propane-1,3-diol;2-(hydroxymethyl)-2-propylpropane-1,3-diol;2-(hydroxymethyl)-2-methylpropane-1,3-diol;2-(hydroxymethyl)propane-1,3-diol;2-(hydroxymethyl)-2-nitropropane-1,3-diol; Trimethylolpropane;2-amino-2-(hydroxymethyl)propane-1,3-diol.

Depending on the transition metal ion, the HεL's, the liquid or polymersolvent used in the LETC system, the following list of LεL's may also beuseful: Di(Trimethylolpropane); L-Fucose; meso-Erythritol;N-propyl-N-pyridin-2-ylpyridin-2-amine; Poly(vinylbutyral);Poly(vinylpyrrolidone); Tetrahydrofurfuryl alcohol;Tetrahydropyran-2-methanol; Triethanolamine; 1,2,4-Butanetriol;1,2-phenylenedimethanol; 1,2-Hexanediol; 1,2-Propanediol;cis,cis-1,3,5-Cyclohexanetriol; 1,3,5-Pentanetriol;2,5-bis(hydroxymethyl)-1,4-dioxane-2,5-diol; 1,4-Butanediol;1,4-Cyclohexanediol; 18-Crown-6; 2,3-Dimethyl-2,3-butanediol;2-Phenyl-1,2-Propanediol; 3-(Diethylamino)-1,2-propanediol;2-ethyl-2-(hydroxymethyl)butane-1,4-diol; 3,3-Dimethyl-1,2-butanediol;3-Hydroxypropionitrile; 3-Methyl-1,3,5-Pentanetriol;3-Phenoxy-1,2-Propanediol; 4-Hydroxy-4-methyl-2-pentanone;3-Phenyl-1-propanol; (5-methyl-1,3-dioxan-5-yl)methanol;Bis(methylsulfinyl)methane; Butyl sulfoxide; Diethylene glycol;Diethylformamide; Hexamethylphosphoramide; 3,3′-oxydipropane-1,2-diol;Dimethyl sulfoxide; Ethanol; Ethylene Glycol; Glycerol; Glycolic Acid;3-(2-methoxyphenoxy)propane-1,2-diol; Lithium Salicylate; LithiumTrifluoroacetate; N,N-Dimethylformamide; 1,1,3,3-Tetramethylurea;2,2-dimethylpropan-1-ol; Pentaethylene glycol; Pentaerythritolethoxylate; tetrahydrothiophene 1-oxide; Tributylphosphine oxide;Trimethylolpropane ethoxylate; Trimethylolpropane propoxylate;Triphenylphosphine oxide.

When the transition metal ion is Ni(II) and the use of water as a LεL isproblematic, α and especially P diols are useful LεL's. A diol is an adiol when two hydroxyl groups are present on adjacent carbons like in2,3-butantediol. A diol is a β diol when two hydroxyl groups are presenton carbons separated by an additional carbon like in 1,3-butanediol. Inmany cases, these α and β diols act as bidentate ligands and they aremore useful than triols because the diols, especially β diols, givehigher positive values of ΔH° and ΔS° for LETC reactions involvingNi(II) ions and most HεL's. In most cases the triols act as tridentateligands and occasionally they are as useful as diols with Ni(II) basedsystems because lower concentrations of triols are required which mayresult in easier processing of the systems which involve polymer layers.

In general, triols are useful LεL's for Co(II) ions in applicationswhere the use of water is problematic. Triols may be more useful thandiols with Co(II) because the tridentate nature of the triols allowsthem to better compete for complexation of Co(II) ions and thus formhigher performance TC systems which also comprise most HεL's of interestfor use with Co(II) ions. With Co(II), the amount of diol required tocompete with most HεL's is too high for most practical applicationsinvolving LETC systems in polymer layers. If the concentrationrequirement for LεL is too high, either that amount of LεL is above thesolubility limit or it is difficult to uniformly disperse in the LETClayer. Alternatively, too much LεL may make it difficult to produce aLETC film or sheet, by e.g., extrusion, because of poor physicalproperties like softness, tackiness, streaks and non-uniform thickness.

LΔL character may also be provided by the hydroxyl groups on variouspolyol polymers like hydroxyethyl cellulose, hydroxypropyl cellulose,poly(vinyl butyral), poly(vinyl alcohol) andpoly(hydroxyalkylmethacrylates and acrylates). Some of these polymerseven provide β diol type functionality.

Acceptable concentrations of LεL's are determined by the concentrationsof the transition metal ions and the ratio of HεL's to transition metalions. The temperature range of the application and the effectiveness ofthe LεL, (i.e. the stability constant for the formation of the LεMLC),are also important in determining useful concentrations. A specific LεLand its concentration are often chosen such that the absorbance of theLETC layer is less than 0.2 at 25 C and the absorbance still increasesto greater than 0.8 at 85 C. These absorbance changes are for the activewavelength range, (at least at one of the λ_(max) values), of a HεMLC inthe LETC system.

HεL

Particularly useful HεL's include the halides: chloride, bromide andiodide and pseudohalides like cyanate, thiocyanate, selenocyanate, azideand cyanide. Other particularly useful HεL's include molecules or ionswhich coordinate to transition metal ions through nitrogen, oxygen,phosphorus, sulfur and/or selenium. The preferred HεL's are those whichprovide for the highest ε for the HεMLC formed and those whichparticipate in equilibrium reactions with the transition metal ions andthe LεL's wherein there are high positive values of ΔH° and ΔS° for theoverall LETC reaction. Described herein are particularly highperformance LETC systems involving iodide ions as a HεL. Highperformance LETC systems are also disclosed wherein phosphine moleculeswhich coordinate through a phosphorus are used as HεL's. Examples ofthese phosphine compounds include ethyldiphenylphosphine,triphenylphosphine and tricyclohexylphosphine. Particularly highperformance LETC systems involve phosphinates as HεL's. Particularlyhigh performance LETC systems are also described involving phosphinecompounds and iodide in combination and these HεL's in combination withother HεL's. The present application describes LETC systems in which aHεL is a five membered, heterocyclic, organic ring compound whichcoordinates to a transition metal through nitrogen. These ligands haveadvantages over six membered ring compounds which coordinate throughnitrogen in that they are more likely to allow TC activity at 550 nm,which is near the peak of human eye sensitivity for light. Otheradvantages of various ligands are described below.

Not only do iodide and phosphine compounds like Ph₃P and other triaryl,trialkyl mixed aryl/alkyl phosphines, when used together, form HεMLC'swith large values of ε, we have discovered a special effect where anexcess of Ph₃P can minimize or eliminate undesirable residual color in aTC layer produced with these ligands. Presumably this is because thephosphine compound sequesters a small amount of residual I₂ and thusprevents the appearance of a yellow color due to free iodine. This freeiodine may be the result of air oxidation of iodide during processingand this problem is mitigated when an excess of a phosphine compound ispresent. This synergistic effect with or without the use of seals tominimize the ingress of oxygen has allowed for the use and production ofthese high performance, LETC systems. In addition, it has beendiscovered that even when the phosphine compound is not intended to beused as a ligand, that an amount of phosphine compound less thanstoichiometric to the amount of transition metal ion can be used wheniodide is a used as a ligand. Even these small amounts of phosphinecompound are useful to mitigate the effects of residual color formationduring processing of these TC systems into layers.

Useful concentrations for HεL's are largely dependent on the transitionmetal ion concentrations used in the LETC system. Generally it is usefulto have a HεL concentration as high as is chemically possible and/oreconomically possible. Specifically it is useful that the concentrationratio for the HεL's to transition metal ions be greater than 4 and inmany cases that the ratio be greater than 7. This is the ratio for thetotal concentration of all HεL's, [HεL_(T)], to the total concentrationof all transition metal ions, [Me_(T)], which together could potentiallybe involved in forming HεMLC's. The advantages of high ratios of HεL'sto metal ions are discussed below.

Ligands containing a nitrogen-containing 5- or 6-membered heterocycliccompound that coordinates through the nitrogen atom to the nitrogentransition metal ion in an HεMLC formed between the transition metal ionand the ligand are particularly useful. Examples of these ligandsinclude those having the following structure:

wherein X₁ and X₃ are each independently selected from the groupconsisting of C, C—R, N, and N—R; X₂ is C or C—R; X₄ is C, C—R, N, N—R,O, S or Se; X₅ is C, N, S, C—R, each R is independently selected fromthe group consisting of hydrogen, substituted or unsubstituted straightor branched alkyl, substituted or unsubstituted aryl, aralkyl, andcombinations thereof, provided that optionally two or more R groups maybe joined to form one or more substituted or unsubstituted fusedsaturated or unsaturated ring systems.

Certain HεL's ligands coordinate more strongly and form coordinationcompounds that absorb at certain desirable wavelengths, especially inthe 550 nm region, when there is a nitrogen in a 5 membered ring. Someof these HεL's that are imidazoles, oxazoles, thiazoles or selenazolesare represented by the following structure:

wherein X═N—H, N—R, O, S, or Se and wherein R and R₁ are independentlychosen from straight or branched, substituted or unsubstituted alkyl;substituted or unsubstituted aryl; or substituted or unsubstitutedaralkyl.

Some of these HεL's that are pyrazoles, isoxazoles, isothiazoles, orisoselenazoles are represented by the following structure:

wherein X═N—H, N—R, O, S, or Se and wherein R, R₁ and R₂ areindependently chosen from straight or branched, substituted orunsubstituted alkyl; substituted or unsubstituted aryl; or substitutedor unsubstituted aralkyl.

Some of these HεL's that are benzimidazoles, benzoxazoles,benzothiazoles, or benzoselenazoles are represented by the followingstructure:

wherein X═N—H, N—R, O, S, or Se and wherein R and R₁ are independentlychosen from straight or branched, substituted or unsubstituted alkyl;substituted or unsubstituted aryl; or substituted or unsubstitutedaralkyl.

Some of these HεL's that are indazoles, benzisoxazoles,benzoisothiazoles, or benzoisoselenazoles are represented by thefollowing structure:

wherein X═N—H, N—R, O, S, or Se and wherein R and R₁ are independentlychosen from straight or branched, substituted or unsubstituted alkyl;substituted or unsubstituted aryl; or substituted or unsubstitutedaralkyl.

Other HεL's that coordinate to transition metals though a nitrogen in afive membered ring are imidazo[1,5-a]pyridine; imidazo[1,2-a]pyridine;1,2,4-triazolo[1,5-a]pyrimidine; 2,1,3-Benzothiadiazole;5-azabenzimidazoles; and 4-azabenzimidazoles.

Bidentate HεL's in which heterocyclic nitrogen containing groups arebridged by alkyl, amine, amine-methylene or benzene as a spacer arerepresented by the following structure:

wherein R, R₁, R₂, R₃, and R₄ are independently chosen from straight orbranched, substituted or unsubstituted alkyl; substituted orunsubstituted aryl; or substituted or unsubstituted aralkyl.and wherein each

independently represents a nitrogen-containing five or six membered ringand in certain cases is independently chosen from substituted orunsubstituted imidazole, pyridine, benzimidazole, benzothiazole,indazole, pyrazole, etc.

HεL's that function as tridentate ligands that coordinate with 3nitrogens are represented by the following structure:

wherein X and Y are independently chosen from (CH₂)_(n)=1 to 3;R=straight or branched, substituted or unsubstituted alkyl; substitutedor unsubstituted aryl; or substituted or unsubstituted aralkyl;and each

independently represents a nitrogen-containing five or six membered ringand in certain cases is independently chosen from substituted orunsubstituted imidazole, pyridine, benzimidazole, benzothiazole,indazole, pyrazole, etc.

HεL's that can coordinate in multiple bidentate configurations arerepresented by the following structure:

wherein only 1 or 2 of X, Y and Z are (CH₂)_(n) n=1 to 2 and the othersare a direct bond between N and the ring C, and each

independently represents a nitrogen-containing five or six membered ringand in certain cases is independently chosen from substituted orunsubstituted imidazole, pyridine benzimidazole, benzothiazole,indazole, pyrazole, etc.

HεL's that are ortho hindered pyridines are represented by the followingstructure:

wherein R=halide; substituted or unsubstituted, straight or branchedalkyl; substituted or unsubstituted aryl; or substituted orunsubstituted aralkyl.

HεL's that function as bidentate ligands via an amine type nitrogen andan imine type nitrogen are represented by the following structure:wherein X═(CH₂)_(n) n=1 to 4,

and R, R₁, R₂, R₃, and R₄ are independently chosen from substituted orunsubstituted, straight or branched alkyl; substituted or unsubstitutedaryl; or substituted or unsubstituted aralkyl;and

each independently represents a nitrogen-containing five or six memberedring and in certain cases is independently chosen from substituted orunsubstituted imidazole, pyridine, benzimidazole, benzothiazole,indazole, pyrazole, etc.

In many of the structures above,

may be replaced by —NR₁R₂ where R₁ and R₂ are independently chosen fromsubstituted or unsubstituted, straight or branched alkyl; substituted orunsubstituted aryl; or substituted or unsubstituted aralkyl.

HεL's that coordinate via a mercapto group and an imine type nitrogenare represented by the following structure:

wherein X═N—H, N—R, O, S, or Se and R=substituted or unsubstituted,straight or branched alkyl; substituted or unsubstituted aryl; orsubstituted or unsubstituted aralkyl.

HεL's that are phosphine compounds are represented by the followingstructure:

wherein R₁, R₂ and R₃ are independently selected from alkyl, cycloalkyl,or substituted or unsubstituted aryl.

In many cases, HεMLC's that involve the ligands with the structuresabove, also involve halides or pseudohalides in the same HεMLC's. Otheruseful HεL's are given in the key section of Table 27.

Solvents

In LETC systems, any solvent that provides for and maintains thedissolution of the metal salt complexes and ligands, allows for thechange or exchange of ligands to take place and does not detract fromthe reversibility or stability of the system is acceptable. Some of thesolvents that we have found, which meet these criteria, are liquids at25 C. These include polar organic solvents like acetonitrile,glutaronitrile, 3-methoxypropionitrile, sulfolane,1,1,3,3-tetramethylurea, dimethylsufoxide, hexamethylphosphoramide,ε-caprolactone, dimethylformamide, ethylene glycol, and propyleneglycol. In many cases it is effective to have a relatively indifferentsolvent with respect to metal ion complexation like propylene carbonateor γ-BL so that the LETC equilibrium is established largely by theinteraction of the LεL's, the HεL's and the transition metal ionsdissolved in the solvent.

Other effective solvents, that are polymers, include poly(vinylalcohol);copolymers of poly(vinylalcohol) with vinyl acetate, methylmethacrylate,ethylene and the like; poly(vinyl acetals) including poly(viny butyral);cellulose acetates; urethanes; hydroxyalkylcelluloses;hydroxy-substituted polyacrylates like poly(hydroxyethyl methacrylate)and poly(1-glycerol methacrylate); poly(2-ethyl-2-oxazoline);poly(N-vinylpyrrolidone); poly(vinyl methyl ether); polyacrylamide;poly(N,N-dimethylacrylamide); polyvinylpyridines and various copolymerswhich involve these polymer functionalities. Also useful are solventsystems which involve a combination of one or more than one of thesolvents, which are liquids at 25 C, dissolved in a polymer.Particularly useful are polymers that form solutions of LETC systemsthat will not flow under the influence of gravity alone in thetemperature range of 0 to 100 Celsius. Polymers that form solutions ofLETC systems that are solids in the temperature range of 0 to 100Celsius are particularly useful.

The solvent may also be the solid matrix portion and/or the liquidsolution portion of a gel. In a “chemical gel” there is a liquid phaseand a solid matrix phase. The solid matrix phase may be an inorganicpolymer like in a common sol-gel or it may be an organic polymer whichis crosslinked or a star polymer which forms a three dimensionalnetwork. The liquid phase for a LETC system is preferably one or more ofthe liquids at 25 C listed above. The gel may be a chemical gelincluding a “molecular gel” or a physical gel. For a more detaileddiscussion of gels see: Electrochimica Acta 46, 2015-2022 (2001).

In principle, the solvent may be a molten salt including a lowtemperature or room temperature ionic liquid.

Certain LεL's, especially diols, triols and polyols, are effective inpromoting solubility of other materials in the LETC system. Also, someof these LεL's are good plasticizers for the polymers that serve ascosolvents and matrices in LETC systems.

Types of MLC's

The spectra of many MLC's are relatively well understood; see forexample “Inorganic Electronic Spectroscopy” by A. B. P. Lever, ElsevierPublishing Co. (1968) and (1984) and “Inorganic Chemistry”, 3^(rd)Edition, by G. L. Miessler and D. A. Tarr, Prentice Hall (2004).Generally when a set of ligands coordinates at six sites around themetal ion, the MLC has lower molar absorptivity values in the visibleand NIR. This ligand configuration may be referred to as hexa-coordinateand generally gives the complex an octahedral or nearly octahedralconfiguration. Often, there are some relatively strong absorbances inthe UV even with hexacoordinate complexes due to charge transfer typeabsorptions. However, absorbances due to transitions of electronsbetween molecular orbitals of predominately metal d-orbital character inoctahedral MLC's are generally quite weak. Furthermore, the photonscapable of causing such electronic transitions are almost exclusively inthe visible and NIR. Whether or not a set of ligands gives rise to ahexa-coordinate or octahedral configuration, if a MLC which decreases inconcentration on heating has an ε of less than or equal to 50liters/(mole*cm) throughout the visible and NIR range of 400 nm to 1400nm, then it is hereby defined as a LεMLC.

Generally when a set of ligands coordinates at four sites around themetal ion, the MLC has a higher molar absorptivity in the visible and/orNIR. This ligand configuration may be referred to as tetra-coordinateand generally gives the complex a tetrahedral configuration, a squareplanar configuration or distorted versions thereof sometimes referred toas pseudo tetrahedral or pseudo square planar. Generally, the highermolar absorptivity of these complexes is due to more highly allowedelectronic transitions between molecular orbitals of predominately metald-orbital character. Occasionally the tetra-coordinate complexes havevery strong absorbances due to charge transfer transitions in thevisible portion of the spectrum and we have discovered that these can beused to great advantage in LETC systems. Whether or not a set of ligandsgives rise to a tetra-coordinate configuration, if the MLC thatincreases in concentration on heating has an ε of greater than 50liters/(mole*cm) anywhere in the visible or NIR region then it is herebydefined as a HεMLC.

Given the definitions above for LεMLC's and HεMLC's, a few LETCthermochromic systems of interest actually function by having one HεMLCchange into another HεMLC. In one system like this, the HεMLC thatdominates at lower temperatures absorbs mainly in the NIR and the HεMLCthat dominates at high temperatures absorbs mainly in the visibleportion of the spectrum. See Table 27, entry 359.

Another system like this has a HεMLC that dominates at lowertemperatures with a modest absorptivity in the visible and has a HεMLCthat dominates at high temperatures with a higher absorptivity in theNIR. See Table 27, entries 406, 457, 861 and 901.

Apart from octahedral and tetrahedral configurations, MLC's are known inwhich three, five, seven, eight or even more sites around a metal ionare coordinated. In these cases, we use the same criteria as above todistinguish between them as LεMLC's and HεMLC's.

LεMLC's include Cu(H₂O)₆ ²⁺ and Fe(H₂O)₆ ²⁺. LεMLC's include Ni(II) andCo(II) coordinated by diols, triols or polyols. Some LεMLC's arecoordination compounds with likely formulas: Ni(TMOLP)₂ ²⁺,Ni(2-(hydroxymethyl)-2-methylpropane-1,3-diol)₂ ²,Ni(cis,cis-1,3,5-cyclohexanetiol)₂ ²⁺, Ni(NPG)₃ ²⁺,Ni(2,4-dimethyl-2,4-pentanediol)₃ ², Ni(3-methyl-1,3,5-pentanetriol)₂²⁺, Ni(poly(vinyl butyral))²⁺, Co(TMOLP)₂ ²⁺, Co(NPG)₃ ²⁺,Co(2,4-dimethyl-2,4-pentanediol)₃ ²⁺,Co(cis,cis-1,3,5-cyclohexanetniol)₂ ²⁺, Co(poly(vinyl butyral))²⁺. Inaddition LεMLC's are useful when diols, triols and polyols are at leastpartially coordinated to the transition metal ions as is often the casewith Ni(II) based systems that also contain nitrogen based ligands.

Some HεMLC's include FeBr₄ ²⁻; CoCl₃(S)⁻; CoBr₃(S)⁻; CoI₃(S)⁻;NiCl₃(S)⁻; NiBr₃(S)⁻; NiI₃(S)⁻; CoCl₄ ²⁻; CoBr₄ ²⁻; CoI₄ ²⁻; NiCl₄ ²⁻;NiBr₄ ²⁻; NiI₄ ²⁻; Cu(S)₂Cl₄ ²⁻; complexes of Co(II), Ni(II), or Cu(II)with ligands which coordinate to metal ions through pseudohalides,nitrogen, oxygen, phosphorus, sulfur or selenium; and complexes ofCo(II), Ni(II), or Cu(II) with combinations of halides or pseudohalidesand ligands which coordinate to metal ions through nitrogen, oxygen,phosphorus, sulfur or selenium. The nitrogen, oxygen, sulfur andselenium may be neutral in charge or they may have a formal negativecharge, (i.e. they may be part of an anion). In the above formulas, (S),represents a solvent molecule, a hydroxyl group or an unknown ligand.One, two, three or four halides of the same type or of two or moretypes, (e.g. both bromide and iodide), may be coordinated to the samemetal ion at the same time. Some HεMLC's involve Co(II) or Ni(II)coordinated to ligands based on pyridine derivatives, pyridazines,dipyridyl derivatives, dipyridylamines, imidazoles, bisimidazoles,indazoles, pyrazoles, benzimidazoles, bisbenzimidazoles, phosphines,phosphinates, thiols, thiol ethers and especially these ligands incombination with chloride, bromide and/or iodide. HεMLC's includecomplexes with ligands that may be mono, bi, tri or tetradentate.

HεMLC's include complexes with ligands based on nitrogen as a heteroatomin a five membered, organic, ring compounds. Nitrogen based ligands infive membered rings have been discovered to form LETC systems withhigher performance, more desirable wavelengths of activity, especiallyin the 550 nm region and/or they are lower cost than many ligands basedon nitrogen as a heteroatom from six membered, organic, ring compounds.Cost considerations aside, these advantages may be due to less sterichinderance for involvement by nitrogen from five membered ring compoundsversus those in six membered ring compounds. On the other hand forproviding absorption peaks in certain other wavelength regions HεMLC'sinvolving ligands with nitrogens in six membered rings are still useful.Also, we have discovered HεMLC's with absorption peaks at desirablewavelengths that involve ligands with nitrogens in six membered ringslike pyridine which have a substituent in a position ortho to thenitrogen. These ligands coordinate to transition metals with a strengththat makes them desirable for combining with other HεMLC's that form inthe same solution and give TC activity over the same temperature range.In addition, these ortho substituted pyridine and pyridine like ligandsare less likely to participate in LεMLC's than unhinderd versionsthereof and this results in lower εS for the LεMLC's. Quinoline and itderivatives are naturally ortho substituted pyridines and thus areeffective in forming HεMLC's with these advantages.

Table 1 shows the HεMLC's for thermochromic systems where the HεMLC'sare based on just Ni(II) ions, a few nitrogen containing ligands andbromide. With good LεL's in these TC systems, we obtain large absorbanceincreases with increasing temperature over the range 25 C to 105 C areobtained. Remarkably, these absorbance increases have λ_(max)'s thatrange all the way from 435 nm to 781 nm. TABLE 1 λ_(max) λ_(max) λ_(max)values values values Most Likely HεMLC (nm) (nm) (nm)Ni(N—Pr-dipicoylamine)Br⁻ 435 523 717 Ni(N-Bu-di(1-MeBIMZ-2- 450 544 781ylmethyl)amine)Br⁻ Ni(N—Pr-DPamine)Br₂ 502 557Ni(2,2′-propane-2,2-diylbis(1-propyl-1H- 503 568 benzimidazole)Br₂Ni(2,2′-methylenedipyridine)Br₂ 520Ni(2,2′-ethane-1,2-diyldipyridine)Br₂ 548 610Ni(2,2′-propane-1,3-diyldipyridine)Br₂ 556 636 Ni(1-EtBIMZ)₂Br₂ 580Ni(4-(3-PhPr)Pyr)Br₃ ⁻ 631 Ni(isoquinoline)Br₃ ⁻ 633 Ni(1-EtBIMZ)Br₃ ⁻640 Ni(ROH)Br₃ ⁻ 659 NiBr₄ ²⁻ 706 757Many more examples of LETC systems, with activity at a wide variety ofwavelengths, are given in Table 27.

LETC Reaction Equilibria

Some generalized ligand exchange reactions with monodentate, bidentate,and tridentate LεL's are given by the following equations:Me(mono-dentate)₆ ²⁺+4X⁻

MeX₄ ²⁻+6(mono-dentate)  (2)Me(bi-dentate)₃ ²⁺+4X⁻

MeX₄ ²⁻+3(bi-dentate)  (3)Me(tri-dentate)₂ ²⁺+4X

MeX₄ ²⁻+2(tri-dentate)  (4)

For the present disclosure all of the LETC equilibria reactions arewritten such that the LεMLC is on the left and HεMLC is on the right ofthe mass balance, equilibrium equation. In equilibria reactions (2)through (4), X⁻ is a HεL and the metal ion is changing fromhexa-coordinate to tetra-coordinate. The change from hexa totetra-coordinate is useful but is not required in LETC systems.

As used herein, transition metal ions in solution are always consideredto be complexed or ligated, since even when free in solution, transitionmetal ions are considered to be coordinated by the solvent. However,ligands may participate in a complex or they may be free in solutionwhere the ligands are not coordinated but are simply solvated. Thus,with many LETC systems like those above, the ligand exchange is simplybetween one type of LεL either being ligated to a metal ion or beingfree in solution and one type of HεL either being free in solution orbeing ligated to a metal ion. A specific example of just one of thetypes of equilibrium reactions that fit the above description is givenbelow:Ni(TMOLP)₂ ²⁺+4Cl⁻

NiCl₄ ²⁻+2(TMOLP)  (5)

-   -   (light green) (blue)        NiCl₄ ²⁻ is a well know MLC from the literature and it is a        HεMLC. Ni(TMOLP)₂ ²⁺ is a LεMLC. It is unlikely that the        reaction in equation 5 proceeds in a single step. However in        many cases the observed changes in absorbance with temperature        point to a main or predominant overall reaction like that shown        in equation (5).

Under some conditions with, for example, a cobalt-halide system, theobserved spectral changes point to equilibria that are bit less straightforward. In the specific case in equation (6) below, the LεL,1,3-butanediol, of the LεMLC may remain partially coordinated to theCo(II) and thus participate in the HεMLC. This is represented by the1,3-butanediol_(mono) in the formula below. For the sake of convenience,the partially coordinated diol is now said to be a HεL. The bromide, onthe other hand, is the primary HεL and when the bromide is notcoordinated to the Co(II) it appears on the same side of the equation asthe LεMLC, Co(1,3-butanediol_(bi))₃Co(1,3-butanediol_(bi))₃ ²⁺+3Br⁻

Co(1,3-butanediol_(mono))Br₃ ¹⁻+2(1,3-butandiol)  (6)

-   -   (light pink) (blue)

Here the term 1,3-butanediol_(bi) is used to designate the1,3-butanediol as acting as a bidentate ligand and the term1,3-butanediol_(mono) is used designate a 1,3-butanediol molecule stillattached to the Co(II) but now in a monodentate fashion whereessentially one hydroxyl oxygen is still coordinated.

More involved LETC reaction equilibria yet are represented by thefollowing equations:Ni(N—Pr-DPamine)(NPG)₂ ²⁺+4Cl⁻

NiCl₄ ²⁻+(N—Pr-DPamine)+2NPG  (7)Ni(N—Pr-DPamine)₃ ²⁺+4Cl⁻

NiCl₄ ²⁻+3N—Pr-DPamine  (8)Ni(N—Pr-DPamine)Cl₂+2Cl⁻

NiCl₄ ²⁻+N—Pr-DPamine  (9)Ni(N—Pr-DPamine)(NPG)₂ ²⁺+2Cl⁻

Ni(N—Pr-DPamine)Cl₂+2NPG  (10)Ni(N—Pr-DPamine)₃ ²⁺+2Cl⁻

Ni(N—Pr-DPamine)Cl₂+2(N—Pr-DPamine)  (11)

From the best of our understanding of this system,Ni(N—Pr-DPamine)(NPG)₂ ²⁺ and Ni(N—Pr-DPamine)₃ ²⁺ are possible LεMLC's.The amount of each of these LεMLC's present depends on the relativeamounts of Ni(II) and especially the relative amounts of NPG andN—Pr-DPamine to each other and to the amount of Ni(II). However, thespectra at lower temperatures do not appear to show the presence ofNi(NPG)₃ ²⁺ when there is one N—Pr-DPamine per Ni(II) present. This isthe case even with an excess of NPG present. This is unfortunate in thatthe absorption coefficient for Ni(N—Pr-DPamine)(NPG)₂ ²⁺ is somewhathigher than that of Ni(NPG)₃ ²⁺. This is very similar to the absorbanceshown in FIG. 18 at 25 C in the 550 nm to 775 nm region for the verysimilar LETC system with Ni(II), N—Pr-DPamine, bromide and TMOLP.LεMLC's like Ni(N—Pr-DPamine)(NPG)₂ ²⁺ result in more absorbance or adarker color than desired at lower temperatures even though the systemhas reasonably good performance otherwise due to a significant increasein absorbance or a darkening in color as the temperature increases.

In the system of equations (7)-(11), NPG is a LεL and chloride is a HεL.N—Pr-DPamine is both a LεL and a HεL. NiCl₄ ²⁻ and Ni(N—Pr-DPamine)Cl₂are HεMLC's. With properly chosen levels of chloride, NPG andN—Pr-DPamine, either NiCl₄ ²⁻ is the main HεMLC formed on heating or itis possible that heating results in an absorbance increase that can beattributed almost exclusively to the complex: Ni(N—Pr-DPamine)Cl₂.Remarkably, these HεMLC's can also form simultaneously on heating overthe same temperature range with the properly chosen concentrations andratios of the materials in equations (7)-(11). Despite the rathercomplicated equilibria possible, this system illustrates the diverseperformance possible when concentrations and concentration ratios arejudiciously adjusted.

As shown above, a ligand that is primarily used as a HεL may remain inplace in the LεMLC. This is the case with many heterocyclic ligands inwhich nitrogen is the heteroatom. For example, solutions of Ni(II) withbromide and 1-EtBIMZ, appear to form two different HεMLC's each of whichis a different shade of blue. One of these complexes is believed to havetwo bromides and two of the benzimidazoles coordinated to the nickel andhas significant absorbance at 550 nm. The other is believed to havethree bromides and one benzimidazole coordinated to Ni(II) and haslittle absorbance at 550 nm. Addition of a good LεL like TMOLP to asolution containing either or both of these complexes decreases theintensity of the blue color. However, a small, (but significant withregard to overall performance), absorption peak at about 640 nm remainseven with a large excess of TMOLP. An absorption peak with this shapeand apparent molar absorptivity is not present for Ni(II) complexed withTMOLP alone or when Ni(II) and bromide are present with or withoutTMOLP. This suggests that at least one, difficult to displace, moleculeof 1-EtBIMZ is present in the LεMLC. While the 1-EtBIMZ is present inthe LεMLC, it is designated as a LεL. Heating a system with appropriateratios and amounts of Ni(II), bromide, 1-EtBIMZ and TMOLP contained inan indifferent solvent or polymer matrix gives a change from light blueto various shades of dark blue. This change in absorbance is presumed tobe due to the increase in concentration of the HεMLC's: Ni(1-EtBIMZ)₂Br₂and/or Ni(1-EtBIMZ)Br₃ ⁻. Depending on the relative concentrations ofNi(II), bromide and 1-EtBIMZ the presumed LETC reactions are those shownin equation (12) or (13) or a combination of these two reactions asshown in equation (14) below.Ni(1-EtBIMZ)(TMOLP_(tri))(TMOLP_(bi))²⁺+3Br⁻

Ni(1-EtBIMZ)Br₃ ⁻+2(TMOLP)  (12)Ni(1-EtBIMZ)(TMOLP_(tri))(TMOLP_(bi))²⁺+2Br⁻+1-EtBIMZ

Ni(1-EtBIMZ)₂Br₂+2(TMOLP)  (13)2Ni(1-EtBIMZ)(TMOLP_(tri))(TMOLP_(bi))²⁺+5Br⁻+1-EtBIMZ

Ni(1-EtBIMZ)Br₃ ⁻+Ni(1-EtBIMZ)₂Br₂+4(TMOLP)  (14)

TMOLP_(tri) and TMOLP_(bi) represent TMOLP acting as a tridentate ligandand as a bidentate ligand where only two of its hydroxyls arecoordinated, respectively. The relative amount of Ni(1-EtBIMZ)₂Br₂versus Ni(1-EtBIMZ)Br₃ ⁻ may be adjusted by judicious choices of therelative amount of bromide vs. 1-EtBIMZ in the system. Large amounts ofbromide relative to 1-EtBIMZ favor the formation of NiBr₃(1-EtBIMZ)⁻,however even very large excesses of bromide do not result in theappearance of the spectra of species like NiBr₃(S)¹⁻ or NiBr₄ ²⁻ whenthere is at least one 1-EtBIMZ molecule per Ni(II) ion present.

Many heteroleptic MLC's are known which involve two or more differentligands on the same transition metal ion, however very few reversible,solution based, thermochromic systems involving ligand exchange to formsuch heteroleptic MLC's have been previously disclosed. Two of thesedisclosed here are shown in the equations (12) and (13) and we havediscovered many more of these systems which are disclosed in Table 27.Through the use of these systems, absorptions can be achieved throughoutthe visible and NIR range which is advantageous from an energy absorbingstandpoint, especially for sunlight blocking applications.

A number of our LETC systems give rise to multiple HεMLC's from theheating of a single composition, even with only a single type oftransition metal ion present. Another good example of this is seen withNi(II), bromide, N—Pr-DPamine with various LεL's. With the proper ratioof bromide to N—Pr-DPamine, heating the system gives rise simultaneouslyto absorption spectra consistent with the presence ofNi(N—Pr-DPamine)Br₂, NiBr₃(S)⁻ and NiBr₄ ²⁻. This type of performancefor a LETC system is shown in FIG. 18. The broad spectral changes thattake place on heating systems like these have distinct advantages whenthere is a desire to relieve glare or reduce energy transmissionthroughout the visible and NIR regions. Broad changes also help providevaluable options for the color appearance of transmitted light. Thesesystems that allow for multiple HεMLC's to form in a single compositionalso provide opportunities to reduce the number of LETC layers requiredfor many applications. Numerous other systems like this are disclosed inTable 27 and several of these systems are shown in FIGS. 4, 14, 17 and28.

Once again, with systems like those in equations (12)-(14), a nitrogencontaining ligand may be present in the LεMLC's. When this is the case,the ε's of the LεMLC are generally larger than if just hydroxyl groupsare present around the metal ion. This higher level of absorptivity is adisadvantage for LETC systems where a large absorbance range is desired.This is because for many applications there is a desire to start with aslittle absorbance or as light a color as possible at low temperaturesand still increase in absorbance or darken in color significantly onincreasing the temperature. However, we have discovered several,nitrogen containing, ligands which do not participate well in a LεMLC.This effect is illustrated by comparing FIGS. 29 and 30. In FIG. 29 thenitrogen containing ligand 6-methyl-2,2′-dipyridyl is believed toparticipate in the LεMLC and give rise to the small but, troublesomeabsorbance between about 575 nm and 750 nm at 25 C. Addition of anothermethyl group to the ligand to give 6,6′-dimethyl-2,2′-dipyridyldecreases the absorbance between 575 nm and 750 nm as shown in FIG. 30.This is because the latter, nitrogen-containing ligand is moresterically challenged in trying to participate in the nominallyoctahedral configuration, while it still participates nicely in thenominally tetrahedral configuration around nickel with two bromide ions.Other nitrogen containing ligands with this advantage include6-methyl-N-(6-methylpyridin-2-yl)-N-propylpyridin-2-amine,6-butyl-6′-methyl-2,2′-bipyridine,2,2′-propane-2,2-diylbis(1,3-benzothiazole),2,2′-propane-2,2-diylbis(1-propyl-1H-benzimidazole),2,2′-propane-2,2-diylbis(1-pentyl-1H-benzimidazole), several6-alkylsubstituted dipyridylamines and to some extent most orthosubstituted pyridines.

Many TC systems involving Ni(II), bromide and nitrogen based ligandshave little absorbance between about 410 nm and 470 nm and thus theyhave a “valley” or a “well” in the absorption spectra in this wavelengthrange even at elevated temperatures. This valley or well makes thesesystems difficult to use in combination with other systems to achievegray appearance in multilayer systems unless the system with which theyare combined happens to absorb in the 410 nm to 470 nm region. Asignificant advantage is realized when there is at least some increasein absorbance in this range as the temperature increases. As illustratedespecially in Examples 18, 36 and 40 and the corresponding figures,there is a TC phenomenon that we call “well-filling”. In contrast, thereare many systems without well-filling as exemplified by Examples 7, 13,19 and 22. While for Examples 18, 36 and 40 there is no absorption peakin the 410 nm to 470 nm region, at least there is an increase in theabsorbance in the valley or well. What the nitrogen based ligands, ineach of these examples, have in common is a nitrogen as a heteroatom ina ring and they also have an amine nitrogen on a carbon alpha to theheteroatom nitrogen which is also the position on the heterocyclic ringthat is ortho to the heteroatom. Thus it is believed that this nitrogenattached to a position ortho to a heteroatom nitrogen, simply called the“ortho-nitrogen” affect, is responsible for the well-filling effect. Thesystems in Examples 18, 36 and 40 are easier to combine into multilayer,gray systems especially with other systems or layers that have peaks inthe 550 nm to 650 nm region which wavelengths also need to be attenuatedto give a gray appearance.

With regard to well filling, it is useful to have thermochromic systemsin which a HεMLC comprises chloride or bromide coordinated to Ni(II)along with another ligand such that the ratio of the HεMLC's maximumabsorption coefficient in the 475 nm to 550 nm range to the HεMLC'sminimum absorption coefficient in the 425 nm to 475 nm range is lessthan 4 to 1. An interesting ligand and TC system is presented in FIG.44. Here the nitrogen containing ligand appears that it might have thepossibility of being tridentate. However the spectra of Ni(II) basedsystems with ligands that are believed to coordinate with threenitrogens plus one or two halides, like examples 8 and 33, have a mainabsorption peak at wavelengths between 430 nm and 460 nm. FIG. 44 showsan example of systems that have spectra more consistent with the ligandacting as two different bidentate nitrogen based ligands. This isobserved even when there is only one of this ligand molecule per Ni(II)ion present in the system. This is believed to be due to the timedependent switching of the coordination of these types of ligandsbetween one type of bidentate configuration and another bidentateconfiguration. In both bidentate cases, in this example, thecoordination is believed to be completed by two bromide ions. Thus thespectra are consistent with (1) a dipyridyl amine with one methylgroup-hindered pyridine and two bromides and (2) two pyridines connectedin ortho positions by an amine-methylene bridge with the pyridineconnected to the methylene group being methyl group hindered and twobromides. The absorptions in FIG. 44 between about 400 nm and 450 nm arebelieved to be more likely due to the ortho-nitrogen affect disclosedabove than to any tridentate character of the6-methyl-N-[(6-methylpyridin-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amineligand. This example discloses a remarkable LETC system in terms of asingle system, with a single ligand other than halide, with good grayappearance, a large change in visible light transmission and littlecolor sweep throughout the temperature range of 25 to 105 C. For thespectra in FIG. 44 we calculate Y to be 82.8, 52.8, 21.4, 9.7 and 6.2 at25 C, 45 C, 65 C, 85 C and 105 C respectively. We also calculate c* tobe 12.9, 17.9, 15.0, 9.7 and 5.7 at 25 C, 45 C, 65 C, 85 C and 105 Crespectively.

Multiple kinds of transition metal ions in the same LETC solution orlayer can give rise to at least two types of useful behavior. One typeis illustrated in FIG. 3 in which ions of one kind of metal are largelyin a HεMLC throughout the temperature range of interest and ions of theother kind of metal switch from largely being in a LεMLC at lowertemperatures to largely being in a HεMLC at a higher temperature. InFIG. 3 it appears that the Co(II) has a higher affinity for iodideand/or a lower affinity for TMOLP as spectral peaks consistent with CoI₄²⁻ remain at nearly constant magnitude throughout the 25 to 105 degreeCelsius range. On the other hand, the amount of Ni(II) coordinated byiodide appears to increase and the amount coordinated by TMOLP isbelieved to decrease as the temperature increases. The spectral peakwith a λ_(max) at about 508 nm is consistent with a charge transfer peakin the visible for NiI₄ ²⁻. The system in FIG. 3 has significantadvantages when used in Sunlight Responsive Thermochromic, SRT™, windowsas the nearly temperature independent absorbance of CoI₄ ²⁻ is largelyin the NIR and causes the system to warm on sunlight exposure. The sunexposure induced temperature rise causes an increase in theconcentration of NiI₄ ²⁻ and a decrease in visible light transmission.Any other thermochromic layer in contact with a layer containing thissystem would also increase in temperature and broad visible lightattenuation is possible just from direct sunlight exposure.

The other type of multiple metal ion system is shown in FIG. 10. This isan example of systems where the temperature dependence for the formationof completely different complexes, even involving different kinds oftransition metal ions, allows for the simultaneous formation of multipleHεMLC's of the different kinds of transition metals ions over the sametemperature range, in the same solution. Heating this system causes anincrease in concentration for two HεMLC's at the same time. TheseHεMLC's might be Co(glycerol_(mono))Cl₃ ⁻ and Cu(glycerol_(di))Cl₄ ²⁻.The use of ZnCl₂ in this system is explained in the next paragraph.

Disclosed herein is yet another new type of thermochromic reaction.Here, ligands may exchange between being coordinated or ligated to afirst kind of metal ion and being coordinated or ligated to a secondkind of metal ion. The second kind of metal ion is a transition metalion that forms a HεMLC which includes a ligand previously associatedwith the first kind of metal ion. For the purposes of the presentapplication, the first kind of metal ions are called exchange metals.The exchange metal may be a transition metal or another kind of metal.In “exchange metal” TC systems, ligands which are ligated or coordinatedto one metal shift to being ligated or coordinated to another metal withchanges in temperature. As the ligands shift from one kind of metal toanother kind there are changes in the light absorption of the system.This is particularly effective when the MLC with one of the metals has asignificantly lower molar absorptivity than the MLC with another metalfor the same type of ligands or set of ligands. Zn(II) ions work well inexchange metal TC systems as the MLC's of Zn(II) often absorb little orno visible light and it has been discovered that the ligands in Zn(II)MLC's readily shift to other metal ions such as Co(II), Ni(II) andCu(II) ions as the temperature of the system increases. Exchange metalsfunction in place of or are used in combination with LεL's.

Another example of an exchange metal TC system is shown in FIG. 11 forthe proposed equilibria:4ZnCl₄ ²⁻+Cu(γ-BL)₆ ²⁺

Cu(γ-BL)₂Cl₄ ²⁻+4Zn(γ-BL)Cl₃ ⁻  (15)Once again the reversible, thermally induced shift in the equilibriumequation gives rise to a LETC process. In this case the chloride isstill the HεL since it is the ligand in the HεMLC. In this case γ-BL isbelieved to play the role of the LεL and the exchange metal ion isZn(II). In the solution of FIG. 10, Zn(II) is also used but this time itis in combination with a LεL, glycerol, to allow the simultaneousformation of HεMLC's of two metals at once as described above.

Mn(II) is of particular interest as an exchange metal because even itstetrahedral MLC's have low molar absorption coefficients; see forexample: F. A. Cotton et. al. J. Amer. Chem. Soc. 84, 167-172 (1962).Exchange metal type LETC systems that have been demonstrated or shouldbe considered are based on Mn(II), Ni(II), Co(II), Sn(II), Cd(II),Cu(II), Al(III) and Sb(V). See Examples 179-188 and Table 12 for moredetails.

LETC systems can be combined with essentially any other thermochromicphenomena. A VO₂ or doped VO₂ film may be included on a substrate thatis in contact with a LETC layer on the other side of the substrate.Alternatively, we have discovered that certain thermochromic materialslike ring opening compounds are compatible with some LETC systems andremarkably they can even be incorporated into the same solution orlayer. FIG. 31 shows the thermochromic performance for a LETC system incombination with a compound known as Oxford Blue and FIG. 32 shows thethermochromic performance for another LETC system in combination with acompound known as Ruby Red. Both of these materials are thermochromicbased on a thermodynamic shift in the equilibrium between thering-closed, colorless form and the ring-opened, highly absorbing form.Ruby Red and Oxford Blue are available from James Robinson LTD ofHuddersfield, England and they are also available from Keystone AnilineCorporation of Chicago, Ill.

Thermodynamics of Reversible Equilibria

LETC processes involve reversible reactions in which the extent of thereaction, (or the position of the equilibrium), is determined by thethermodynamic parameters of the reaction, the temperature of the systemand the total concentrations of each of the reactants/products in thesystem. One of the many types of LETC reactions, which are governed by areversible thermodynamic equilibrium reaction, may be represented by thefollowing equation:Me(LεL)_(x)+yHεL

Me(HεL)_(y)+xLεL  (16)wherein x and y are numeric variables that designate the number of LεLand HεL, respectively. In order for the absorption of the system toincrease with increasing temperature the equilibrium must shift to theright in equation (16) as the temperature increases. This would give anet increase in the light energy absorbed since the ε's for the complexMe(HεL)_(y) are larger than the ε's for the complex Me(LεL)_(x) at manywavelengths in the visible and/or NIR range for nearly all of thesystems disclosed herein. In order for the reaction to be reversible thereaction must shift back to the left the same amount as the temperaturedrops back to its original value. The equilibrium constant for thisreaction is given by:K _(eq)=([Me(HεL)_(y) ][LεL]^(x))/([Me(LεL)_(x) ][HεL] ^(y))  (17)where the brackets are used to signify concentration, (although to bemore accurate one could use activities). While the equilibrium constantis “constant” at a given temperature for wide variations inconcentration, there is a different “constant” at each temperature. Thetemperature dependence of the equilibrium constant is determined by thestandard free energy change, ΔG°, of the reaction, which in turn isdetermined by the standard enthalpy change, ΔH°, of the reaction. Thiscan be seen from the following well known equations:ΔG°=ΔH°−TΔS°  (18)ΔG°=−RT ln K _(eq)  (19)K _(eq)=exp(−ΔH°/RT)*exp(ΔS°/R)  (20)

For most of the LETC systems we have discovered, ΔH° of reaction isroughly constant over the temperature range of 0 to 100 Celsius. If weassume the value of ΔH° is actually constant over the temperature rangeof interest, then the magnitude of the change of K_(eq) with temperatureis dependent only on the magnitude of ΔH°. Also, for the equilibrium toshift to the right and for the net sunlight energy absorbed by thesystem to increase with a temperature increase, K_(eq) must increase.This can be seen from the mass balance in equation (16) where the[Me(HεL)_(y)] must increase for the absorbance to increase. Given aconstant total concentration of all the ingredients used to make up thesystem, the only way for the equilibrium to shift to the right is forthe value of the equilibrium constant to increase; see equation (17).The value of K_(eq) increases as the temperature increases only if ΔH°is positive as shown in equation (20). The larger the positive value ofΔH° for the equilibrium reaction the larger the increase in the value ofK_(eq), over a given temperature range, as shown by the followingequations:K _(eq)(T _(H))=exp(−ΔH°/RT _(H))*exp(ΔS°/R)  (21)K _(eq)(T _(L))=exp(−ΔH°/RT _(L))*exp(ΔS°/R)  (22)K _(eq)(T _(H))/K _(eq)(T _(L))=exp((ΔH°/R)*(1/T _(L)−1/T _(H)))  (23)where T_(H) and T_(L) are the high and low temperatures over which theLETC system is being evaluated. Equation (23) is independent of ΔS° andshows that the highest performance for a LETC system, in terms of thelargest increase in light absorption, over a given temperature range,comes with the highest positive value of ΔH°. This is supported by thegraph in FIG. 47 which shows the increase in the ratio of equilibriumconstant values for two different temperatures as a function of ΔH°.This is simply a graph of equation (23) for T_(H) equal 85 C and T_(L)equal 25 C, however it is a powerful illustration of the utility ofhaving high ΔH° for LETC reactions.

However, the larger the positive value of ΔH°, at a given temperatureand a given value of ΔS°, the smaller the value of K_(eq). It may bepossible to have such a large positive value of ΔH° giving such a smallvalue of K_(eq) that even a many fold increase in the value of K_(eq)gives little or no observable light absorption change. This may happenbecause the [Me(HεL)_(y)] is so low that even a many fold increase in[Me(HεL)_(y)] with temperature is still a small concentration. Thus alarge positive value of ΔS° is desirable, (if not necessary), inconjunction with a large, positive ΔH° if a reasonably low concentrationof materials or a reasonably small path length, (layer thickness), is tobe used. In essence, the ΔS° of the equilibrium reaction is important inthat its value helps determine the position of the equilibrium at eachtemperature, while ΔH° determines the temperature dependence. FIG. 48helps illustrate the influence of ΔS° on the effective temperature rangefor absorbance changes for LETC reactions like:Me(LεL)₃+4HεL

Me(HεL)₄+3LεL  (24)

FIG. 48 shows the absorbance calculated for a wavelength where the onlyLεMLC≡Me(LεL)₃ has as ε of 1 liters/mole*cm at a λ_(max) of the HεMLCand the only HεMLC≡Me(HεL)₄ has an ε of 280 liters/mole*cm at a λ_(max)of the HεMLC. The absorbance is calculated as a function of temperatureby first calculating an equilibrium constant at each temperature basedon the ΔS° values shown in FIG. 48 and a ΔH° of the reaction of 60kJ/mol. Then the concentrations of Me(LεL)₃ and Me(HεL)₄ at eachtemperature are calculated based on the equilibrium constant and thevalues: [Me_(T)]=0.2M, [HεL_(T)]=1.6M and [LεL_(T)]=2.5M. Theconcentrations of Me(LεL)₃ and Me(HεL)₄, the values of the 's and a pathlength of 0.075 cm are used to determine absorbance values. FIG. 48confirms that while the overall magnitude of the absorbance change withtemperature is determined by the value ΔH°, the temperature range wherethis absorbance change takes place is highly dependent on ΔS°. FIG. 48illustrates how important it is to find reversible equilibria reactionsnot only with large positive values of ΔH°, but also with appropriatelylarge positive values of ΔS°, if LETC systems are to operate overespecially useful temperature ranges like 0 C to 100 C.

The present application discloses many LETC systems in which not onlyare there large positive values for ΔH° and ΔS°, these values are suchthat there is significant thermochromic activity over the 0 C to 100 Ctemperature range. This has been done by choosing systems which combinetransition metal ions, HεL's, LεL's and solvent systems to give thedesirable values of ΔH° and ΔS° which allow for large absorbance changesover a desirable temperature range. In general a ΔH° value from 40kJ/mol to about 90 kJ/mol for the reversible LETC reaction is useful. Ingeneral it is also useful that the value of ΔS° in J/mol*K be such thatwhen the value in J/mol*K is divided by the value of ΔH° in kJ/mol, thatthe quotient be between 1.5 and 3.5 even though the units of thisquotient may not be meaningful. Thus e.g. if ΔH° is 40 kJ/mol then it isdesirable to have ΔS° between 60 J/mol*K and 140 J/mol*K. Once thesystem, with its thermodynamics, is chosen, we have discovered how tooptimize the system even further by judicious choices of concentrationsand ratios for the constituents involved, especially for relatively thinlayers in polymers. This is illustrated in many of the examples and isdiscussed further below.

Good performance for a chosen LETC system comes when the ratio of thetotal concentration of all HεL's to the total metal ion concentration,[HεL_(T)]/[Me_(T)], is as high as possible. This is illustrated in FIG.49 with a calculation based on a system with the following LETCequilibrium equation for a bidentate LεL and a monodentate HεL:Me(LεL)₃+4HεL

Me(HεL)₄+3LεL  (25)The system is assumed to have the following very realistic parameters:

-   -   ΔH°=50 kJ/mol    -   ΔS°=110 J/mol*K    -   ε(Me(LεL)₃)=1 l/mol*cm at λ_(max) of HεMLC    -   ε(Me(HεL)₄)=280 l/mol*cm at λ_(max) of HεMLC    -   Layer Thickness=b=0.075 cm    -   [Me_(T)]=0.2M

Equation 25 is assumed to be the only equilibrium of interest, which maybe nearly the case for many of our systems, especially those in anindifferent or poorly coordinating solvent. Also assumed are (1) all ofthe metal ions are present in the LεMLC≡Me(LεL)₃ or the HεMLC≡Me(HεL)₄;(2) all of the HεL's molecules are free in solution or part of theHεMLC; and (3) all of the LεL's molecules are free in solution or partof the LεMLC. The thermochromic behavior in many of the figures hereinshows these assumptions to be reasonable.

For each ratio, R, of [HεL_(T)]/[Me_(T)], the [LεL] was determined whichwould give the system an absorbance of A=0.8 at 85 C based on the aboveparameters, equilibrium equation and the equation:A=ε(Me(LεL)₃)*b*[Me(LεL)₃]+ε(Me(HεL)₄)*b*[Me(HεL)₄]  (26)The value of [HεL_(T)] is determined by the value of R being used andthe specified [Me_(T)]. The [LεL] values that were determined and thenused are shown in FIG. 49. Using these [LεL]'s, the absorbances atvarious temperatures throughout the 25 C to 85 C range were calculatedfor each ratio of [HεL_(T)]/[Me_(T)]. Then the absorbances versustemperature were plotted in FIG. 49. This graph shows that there issignificant improvement in absorbance change over this temperature rangeas the ratio of [HεL_(T)]/[Me_(T)] is increased even though the requiredamount of LεL also increases.

In many practical applications there is a desire to have a TC layer asthin as possible. LETC systems with thicknesses in the range of 0.02 to0.5 cm with reasonable to excellent performance are disclosed herein. Toachieve high performance in thin films a relatively high concentrationof metal ions should be present. However, there is a trade-off betweenhow high the metal ion concentration needs to be and the desire for alarge ratio of [HεL_(T)] to [Me_(T)], especially when solubility limitsare taken into account.

As discussed before, the theoretical minimum metal ion concentrationsdepend on (1) the desired level of absorbance at an elevated temperatureand a particular wavelength or series of wavelengths, (2) the pathlength, (layer thickness), of the LETC system and (3) the ε of theHεMLC. If an absorbance of at least, A(T_(H), λ), is desired at a highertemperature of operation at some λ, then the minimum metal ionconcentration must be greater than or equal to A(T_(H), λ)/(ε(HεMLC,λ)*b); where b is the path length or layer thickness in centimeters.Practically, we have discovered that the preferred minimum [Me_(T)] is1.5 times the theoretical minimum.

By analogy to the previous analysis, the maximum [Me_(T)] to be used isless than or equal to A(T_(L), λ)/(ε(LεMLC, λ)*b). Thus usefultransition metal ion concentrations are given by the following range:A(T _(L),λ)/(ε(LεMLC,λ)*b)>[Me]>1.5*(A(T _(H),λ)/(ε(HεMLC,λ)*b))  (27)where A(T_(L), λ) is the desired absorbance at λ at some lowertemperature, T_(L), and A(T_(H), λ) is the desired absorbance at λ atsome higher temperature, T_(H).

Of course the total metal ion concentration, [Me_(T)], is alsoconstrained by the solubility limit of the LεMLC's and the HεMLC's inthe system over the temperature range of operation as all of the Me inthe system is either in LεMLC's or HεMLC's. The [Me_(T)] is alsoconstrained by the ability of the system to provide an adequate [HεL].Thus the useful [Me_(T)] is also determined by:[Me _(T)]<0.25*(solubility limit of [HεL])  (28)

Reasonably good, although still approximate, values for can be foundwith a known metal ion concentration and an appropriate excess of LεL orHεL so that essentially all of the metal is converted to or is presentin the LεMLC or the HεMLC form. The measured absorbance divided by thepath length and the total metal ion concentration provides useful valuesof ε(LεMLC) and of ε(HεMLC). The following approximate ε values, mostlyin γ-BL, were determined by such a procedure and can be used tocalculate maximum and minimum preferred [Me_(T)] in a variety of LETCsystems since the value of ε for coordination compounds is notparticularly sensitive to the solvent involved: TABLE 2 LεMLC λ_(max)(ε)λ_(max)(ε) λ_(max)(ε) λ_(max)(ε) Ni(NPG)₃ ²⁺ 395(7) 660(3) 720(3)1194(4) Ni(TMOLP)₂ ²⁺ 383(6) 630(2) 711(2) 1097(3) Ni(water)₆ ²⁺ 396(6)661(2) 726(3) 1163(3) Ni(DMSO)₆ ²⁺ 420(10) 695(3) 784(3) 1177(3) Co(EG)₃²⁺ 518(9) Co(γ-BL)_(x) ²⁺ 518(11) Co(PC)_(x) ²⁺ 516(10) Co(18-crown-6)²⁺519(8) Co(bis(methylsulfinyl methane)₃ ²⁺ 546(8)λ_(max) is a wavelength of maximum absorbance in nanometersε is the molar absorption coefficient in liters/(mole * cm)

TABLE 3 HεMLC λ_(max)(ε) λ_(max)(ε) λ_(max)(ε) λ_(max)(ε) λ_(max)(ε)CoCl₄ ²⁻ 635(475) 670(660) 695(810) CoBr₄ ²⁻ 642(235) 666(695) 700(1025)  724(1210) CoI₄ ²⁻ 696(410) 724(775)  782(1930) Co(Bu₃PO)₄ ²⁺560(205) 607(305) 634(360) Co(CF₃COO)₄ ²⁻ 535(125) 572(175)Co(salicylate)₄ ²⁻ 538(235) 577(360) Co((4-MeOPh)₂PO₂)₂ 561(220)590(295) 608(315) 639(360) NiCl₄ ²⁻ 658(205) 704(210) NiBr₄ ²⁻ 709(285)757(295) NiI₄ ²⁻  508(1650) 835(440) Ni(1-EtBIMZ)₂Br₂ 580(220)Ni(1-EtBIMZ)Br₃ ⁻ 640(255) Ni(4-(3-PhPr)Pyr)Br₃ ⁻ 639(225) Ni(N—Pr-435(155) 717(45) dipicolylamine)Br₂ Ni(N-Bu-di(1-MeBIMZ- 448(140)770(35) 2-yl-methyl)amine)Br₂ Ni(Ph₃P)₂Br₂ 590(195) 911(250) 1139(50) Ni(Ph₃P)₂I₂  419(4520)  498(1800)  561(1730) 709(345) 747(410)Ni(TTCTD)²⁺ 500(370)λ_(max) is a wavelength of maximum absorbance in nanometersε is the molar absorption coefficient in liters/(mole * cm)

Given the advantages of large ratios of [HεL_(T)]/[Me_(T)], and thedesire for high [Me_(T)] and the desire for thin layer LETC systems, itbecomes important to find highly soluble versions of HεL's. Fortunately,we have found that high, effective concentrations of halides in polymersystems may be achieved when ammonium and phosphonium cations that aretetrasubstituted are used. The substituents on nitrogen or phosphorusmay be alkyl, aryl or combinations thereof.

After consideration of [Me_(T)] and [HεL_(T)], comes [LεL_(T)]. In fact,when high concentrations of [Me_(T)] and [HεL_(T)] are used, thelimitation on the practicality of the system may depend on thesolubility limit or physical properties imparted by the LεL(s). As longas the [LεL_(T)] is below its solubility limit and the limit wherephysical properties of the system become unacceptable, the specific LεLand its concentration are preferably chosen such that the absorbance ofthe LETC system, (even when the system is a thin polymer layer), is lessthan 0.2 at 25 C while the absorbance still increases to greater than0.8 at 85 C. These absorbances are for the active wavelength range of TCactivity for the particular LETC system. These ranges of TC activity areillustrated in FIGS. 1-46 in liquid solution with a large, (1 cm), pathlength. However, more remarkable are the results in FIGS. 51-58 forpolymer layers with thicknesses from 0.031 to 0.098 cm. Many more rangesof absorbance changes are given in Table 27.

Thus, a high metal ion concentration is desirable as long as it ispossible to still have large a ratio of [HεL_(T)]/[Me_(T)] and aconcentration of LεL high enough to provide a desirable absorbancerange. Another advantage of having large values for [HεL_(T)] and[LεL_(T)] can be seen by considering the mass balance and equilibriumequations below.Me(LεL)_(x) +yHεL=Me(HεL)_(y) +xLεL  (29)K _(eq)=([Me(HεL)_(y) ][LεL] ^(x))/([Me(LεL)_(x) ][HεL] ^(y))  (30)

If the [HεL_(T)] and [LεL_(T)] are both large relative to [Me_(T)], thenthe concentrations of free, non-coordinated HεL and LεL change only asmall amount during a temperature induced shift in equilibrium. Smallpercentage changes in concentration of non-coordinated LεL and HεLduring a temperature induced shift in equilibrium corresponds withlarger changes in [Me(HεL)_(y)] and [Me(LεL)_(x)] than would be achievedotherwise. Thus when the ratio of HεL to metal ion is large and at thesame time there is a large and appropriate concentration of LεL oneobtains the highest performance for the system over a given temperaturerange.

Polymers

In LETC systems, polymers may provide a variety of functions. They mayserve as:

-   -   a solvent or cosolvent    -   an indifferent matrix for the rest of the system    -   the solid phase of a gel    -   some or all of the LεL character    -   some or all of the HεL character    -   a laminating material which may also provide shatter resistance    -   TC or non-TC plastic substrates which may serve as window panes    -   separator layers    -   barrier layers    -   sealants    -   a combination of the above functions

Polymers for TC Layers

Sometimes polymer layers are referred to as films below a certainthickness and are referred to as sheets above that thickness. The LETClayers of the present invention may be films or sheets and may be freestanding or suspended as a separate layer. Alternatively, the layers maybe placed on a substrate or between substrates or be used to laminatesubstrates together. Remarkably, our LETC reactions take place in solidpolymer based systems fast enough that there is essentially no lag timebetween the temperature change and the change in absorbance, at least onthe time scale of 10 to 20 seconds.

Polymers for LETC layers include: poly(vinylalcohol), poly(vinylbutyral), poly(vinylethylene-co-vinylalcohol), poly(vinylacetate),poly(N-vinylpyrrolidone), urethanes, hydroxyalkylcelluloses,hydroxy-substituted acrylates and their copolymers. Other polymerpossibilities include: poly(2-vinylpyridine), poly(1-glycerolmethacrylate), cellulose carboxymethyl ether salt, cellulosehydroxyethyl ether, poly(2-ethyl-2-oxazoline), poly(hydroxyethylmethacrylate) and its copolymers, poly(vinyl methyl ether),polyacrylamide and poly(N,N-dimethylacrylamide).

One of the polymers, poly(vinyl butyral), (PVB), is made in multiplesteps. Generally, polyvinylacetate is hydrolyzed to remove most of theacetyl groups and form polyvinylalcohol. Then most of the alcohol orhydroxyl groups are reacted with butyraldehyde to forms cyclic acetalgroups. The PVB formed is thus a copolymer sometimes referred to as:poly(vinylbutyral-co-vinylalcohol-co-vinylacetate). PVB for many LETCsystems has a high hydroxyl content and provides substantial LεLcharacter. The cyclic acetal portion of the PVB acts as a good andindifferent solvent for many of the other constituents of the LETCsystem. Preferred hydroxyl content in this case is 18% or greater ofthat originally present in the poly(vinyl alcohol). For a few LETCsystems where little LεL character is required, as for example withiodide and/or phosphine compounds as HεL's, PVB with lower hydroxylcontent is may be used.

PVB is a useful polymer since it is well suited for use in lamination ofglass sheets. However, in the presence of water and possible catalyststhe acetal groups are subject to hydrolysis which would freebutyraldehyde molecules. These molecules could subsequently react withmonomeric LεL's which are β-diols. In this case it is preferred thatwater be removed as much a possible by pre-drying materials to beprocessed, venting during extrusion and/or drying of the LETC layerprior to subsequent use. Also, it is possible to use “monomeric” LεL'sthat are diols, triols or polyols that have β-diol functionality whereinone or both of the hydroxy groups is a secondary or a tertiary alcoholwhich helps prevent this “trans-acetalation” of the cyclic acetalmoieties from the PVB to the other LεL's present. This is particularlyimportant when the other LεL is more effective than the PVB at providingLεL character since the trans-acetalation process may decrease theoverall amount of LεL character in the system. This is shown in thefollowing undesirable reaction scheme:

LETC layers, based on PVB as a polymer matrix, may be effectively mixedand extruded in one step using a twin screw extrusion system. Thisavoids a separate, potential costly or thermally damaging compoundingstep. The twin screw system allows mixing and dissolution of the LETCmaterial in PVB and the use of a gear pump between the end of theextrusion barrel and a film forming die allows the production of highquality films. The materials may be pre-dried and the extruder may bevented to allow additional water and other gases to be removed from thepolymer prior to and during production of LETC layers. The materialsthat are fed into an extruder may be purged with an inert gas likenitrogen or argon. However, a LETC layer in PVB may be produced withoutthe need for inert atmosphere conditions in the feed process as long asthe extruder and die temperatures are kept below 150 C. The use ofprocessing temperatures below 150 C is particularly advantageous insystems where iodide and/or phosphine compounds are used as HεL's toprevent irreversible discoloration in the layer produced. Above thistemperature, the performance of the LETC layer produced may be seriouslycompromised.

Substrates

A substrate may serve as a mechanical support for LETC system or layerswhen they are not free standing by themselves. However, substrates arenot considered part of the LETC system unless the LETC system itself isa free standing plastic sheet. If a LETC system is soft and has littlestructural integrity, it may simply be coated on a substrate.Alternatively, a pair of substrates, generally each made out of the samematerial, may be laminated together with a LETC layer which comprises apolymer. Here the substrates provide mechanical support and provide asymmetrical configuration that is not prone to bowing on heating. Bowingis minimized when the thermal expansion coefficients of the substratesare the same or closely matched. The laminate formed by two substratesbonded together with a LETC layer may act a safety or impact resistantwindow pane. This is especially valuable for bullet resistant andhurricane resistant window panes. In a laminate configuration thesubstrates may act as barriers to the ingress of oxygen, water and othercontaminates over the area of the LETC layer. To provide an overallbarrier, the edges of the laminate may be sealed.

Useful substrates include plastics and glass. Useful plastics for use assubstrates include acrylic and polycarbonate sheets. Useful glass sheetsare float glass or drawn sheets. Useful glass sheets for use assubstrates are ones that have been have been cut very cleanly or haveedge treated by seaming, grinding, mechanical or flame polishing and/or“pencil” edging so they resist cracking when heated. Also useful areglass sheets which have been heat strengthened, heat tempered orchemically tempered so that they also resist cracking when heated,especially when non-uniformly heated.

An approach has been developed in which a PVB film is bonded on one sideof a tempered or heat strengthened sheet of glass and a thin film ofplastic film is bonded to the PVB to provide a good optical qualitysurface. Examples of the thin plastic films are polyester, poly(esterterephthalate), poly(acrylic) or poly(carbonate). The thin plastic filmmay have an “excited” surface or adhesion promoting coating on the sideto be bonded to the PVB. Excited surfaces may be provided by plasma,corona or ozone treatment. The thin plastic film may optionally becoated with a low emissivity or NIR reflective coating on one or both ofits surfaces. This structure was prepared with tempered glass and itwithstood temperature ranges from −40 C to +100 C without warping,bowing or delaminating. Even a thermo-shock test on going directly froma freezer at −40 C to +100 C did not cause breakage or delamination. Thecombination of using tempered or heat strengthened glass, PVB with goodthermal expansion/contraction characteristics and a thin plastic filmwith an excited surface has allowed for this advantageous light weight,low cost and highly durable structure.

Plasticizers

LETC systems, contained in polymers, benefit from the presence ofplasticizers. The benefits include ease of processing in for example anextrusion process including lower extrusion temperature, lower torqueand better mixing. Plasticizers increase ease of product handling as thelayers produced with plasticizers are easier to roll-up and processlater in, for example, a lamination process or a pre-lamination process.

The plasticizers may be any material known in the art of plastics andpolymer processing as a good plasticizer for the particular polymer inwhich a LETC system is contained, as long as the plasticizer does notseriously degrade the performance or durability of the LETC system. Forexample, if the polymer is poly(vinyl butyral), conventionalplasticizers are found in the art and include diesters of triethyleneglycol, of tetraethylene glycol, of adipic acid or of phthalic acid.

Plasticizer character is also provided by materials not conventionallyused as plasticizers. Thus, diols and triols, in the amount normallyused to provide LεL character, are effective plasticizers. In addition,quaternary ammonium and quaternary phosphonium halides are alsosurprisingly good at plasticizing LETC polymer layers. Theseligand-plasticizers are effective in plasticizing poly(vinyl butyral) sothat it is easier to process into a film or sheet by extrusion at lowertemperatures and the films or sheets are easier to process furtherespecially when it comes to lamination of the LETC layer between sheetsof glass or making a pre-laminate with a separator layer as describedbelow.

Other unconventional plasticizers that not only help provide enhancedprocessing and desirable physical properties to the LETC layers producedmay also provide enhanced solubility for LETC system components. Theseunconventionally plasticizers include solvents like: acetonitrile,glutaronitrile, 3-methoxypropionitrile, sulfolane,1,1,3,3-tetramethylurea, dimethylsufoxide, hexamethylphosphoramide,propylene carbonate, γ-butyrolactone, ε-caprolactone anddimethylformamide.

While liquids may be used as plasticizers, we have found that there aretimes when it is useful to have a plasticizer that is a solid powder atroom temperature. This allows the plasticizer to be physically mixedinto the polymer resin without causing the mixture to become sticky anddifficult to feed from a feed hopper into the feed throat of anextruder. Particularly useful materials that act as plasticizers and aresolids at room temperature are the LεL diols and triols which are roomtemperature solids. Some of these with their melting points are givenbelow. TABLE 4 Plasticizer/LεL m.p. pentaerythritol 255-259 C.2-(hydroxymethyl)-2-methylpropane-1,3- 200-203 C. diol TMOLP  60-62 C.2-(hydroxymethyl)-2-propylpropane-1,3- 100-102 C. diolcis,cis-1,3,5-cyclohexanetriol, dihydrate   113 C. NPG 124-130 C.2,2-dibutyl-1,3-butanediol  41-43 C. 2,2-diethyl-1,3-butanediol  59-61C. 2-butyl-2-ethyl-1,3-propanediol  41-44 C.

Stabilizers and Additives and Barriers

Stabilization of LETC systems involves preventing or minimizingdegradation due to heat and/or light induced reactions of materialswithin the system or reactions with materials which come from theenvironment. Of course the best approach to stability is to findmaterials that are inherently high in stability and we have discoverednumerous LETC systems with good to excellent inherent stabilityincluding certain systems involving Ni(II) coordinate by iodide andNi(II) coordinated by iodide in combination with other ligands. Somewhatless desirable than good inherent stability is to provide barriers andseals against the ingress of things that contribute to degradation,especially oxygen, water and ultraviolet light. This approach isdiscussed below with regard to barriers and in the section on seals.Even less desirable, yet still an important approach, is to provideadditives which help deal with degradation processes via competitivelight absorption, tying up degradation products or inhibiting furtherdegradation.

LETC systems described herein exhibit excellent inherent stability. Manyof these systems have been exposed to temperatures of 80 C for more than10,000 hours with little or no degradation. Also, thermal stabilizershave been found which are compatible with the LETC systems and provideenhanced thermal stability. These include antioxidants and free radicalinhibitors such as the hindered phenols. Some useful thermal stabilizersinclude 2,6-di-tertbutyl-4-methylphenol, (BHT), Irganox® 245, Irganox®1010, Irganox® 1035, Irganox® 1076 and Irganox® 5057. The Irganox®materials are available from Ciba Specialty Chemicals Corporation ofTarrytown, N.Y.

Photodegradation, especially from short wavelength light, (like UV andshort wavelength visible light), is an issue for many chromogenicsystems including at least some LETC systems. Short wavelength light maybe blocked by an absorbing barrier placed between a vulnerable layer anda source of UV and short wavelength visible light like the sun. Multiplelayers of LETC systems are used in some cases to achieve broad spectralcoverage and a particular color appearance, especially a grayappearance. A highly advantageous configuration for the multilayer LETCsystems is described below. This involves placing UV absorbing materialsin a layer which itself is less vulnerable to photodegradation. Thislayer is then placed between a source of short wavelength light andlayers which are more vulnerable to photodegradation. Other advantageousconfigurations involve a short wavelength light absorbing barrier beingprovided by a substrate layer or even by a separator layer placedbetween the light source and the more vulnerable layers. The advantagesof these configurations should not be underestimated, especially whenone considers the difficulty in providing effective light absorbingbarriers for most chromogenic systems.

Short wavelength absorbing additives, sometime called “UV absorbers”,may be divided into two groups. The first group includes materials whichsimply absorb short wavelength light. Materials of this group areethyl-2-cyano-3,3-diphenylacrylate and(2-ethylhexyl)-3,3-diphenylacrylate available from BASF Corporation ofRensselaer, N.Y. as Uvinul 3035 and Uvinul 3039 respectively. The secondgroup involves absorbers of short wavelength light which also functionas stabilizers against the propagation of degradation initiated by lightexposure. Materials of this group are hydroxybenzophenones,hydroxyphenylbenzotriazoles and hydroxyphenyltriazines. Examples ofthese materials sold under the trade names: Tinuvin® P, Tinuvin® 213,Tinuvin® 234, Tinuvin® 326, Tinuvin® 327, Tinuvin® 328, Tinuvin® 400,Tinuvin® 405 and Tinuvin® 479. These materials are available from CibaSpecialty Chemicals Corporation of Tarrytown, N.Y. Also useful arenickel salt stabilizers like dialkyldithiocarbamates which are good UVabsorbers even though they are bit yellow in polymer films.

Also useful are nickel salt stabilizers likebis(dialkyldithiocarbamates)Ni(II) which are good UV absorbers eventhough they are bit yellow in polymer films. While these materials weregenerally considered to only be good absorbers, there is some literatureto support the possibility that these material may also participate instabilization by chemical means.

These short wavelength absorbing additives, not only promote stabilityas part of LETC system or layer, they can be added to a polymer like PVBand extruded in a film with excellent UV barrier properties. Barrierfilms with a cutoff of about 390 nm have been prepared with 0.5 weight %Tinuvin® 326 in an approximately 500 micron thick layer of Butvar® B-90which was plasticized with tri(ethylene glycol) bis(2-ethylhexanoate). Acutoff of about 400 nm is obtained under similar conditions with 1weight % Tinuvin® 326 in a similar film.

Any of the UV absorbing materials disclosed herein may be used as shortwavelength absorbers in barrier layers, LETC layers, plastic substratesand separator layers. However, some of the second group UVstabilizer/absorber materials are somewhat effective at complexing tometal ions and these complexes are not always stable with time.Therefore when materials from the second group are added directly toLETC systems or layers it is useful to choose the materials which aresterically hindered against strong complex formation or are inherentlypoor complexing agents. The more useful materials from group two in thiscase are Tinuvin® 213 Tinuvin® 234 Tinuvin® 326, Tinuvin® 327, Tinuvin®328, Tinuvin® 400, Tinuvin® 405 and Tinuvin® 479.

FIG. 42 is a good illustration of the addition of UVabsorber/stabilizers directly to a LETC system. Here the Tinuvin® 405does not appear to interfere by coordinating the Ni(II) ions. Also, FIG.42 shows that the absorbance of the system is very high at wavelengthshorter than about 380 nm. This system is thus a great barrier for anysystem that might be behind this system when it is exposed to sunlight.

Also effective in helping stabilize LETC systems and short wavelengthabsorbing barriers are light stabilizers that themselves are not veryeffective at absorbing short wavelength light. Preferred materials ofthis type are hindered amine light stabilizers, (HALS). Useful HALSinclude Tinuvin® 144, Tinuvin® 765 and Tinuvin® 770 available from CibaSpecialty Chemicals Corporation of Tarrytown, N.Y.

The present application also discloses the use of the inherent or thethermally induced short wavelength absorbing ability of LETC systemslike those involving nickel ions and bromide ions. As seen in FIGS. 1and 54, LETC systems like these provide outstanding absorption of shortwavelength light especially at higher temperatures. These LETC systemsor layers may be used to protect layers that are more vulnerable tocombined thermal and photodegradation. Also some of these layers withNi(II) and bromide are inherently photostable on their own so they arebetter suited to being exposed to sunlight and acting as barriers infront of many other more UV sensitive LETC systems.

UV barriers were found to be effective in extending the useful life ofLETC systems. In particular, when a thermochromic like that of FIG. 52was laminated between pieces of plain glass, the laminate had less than2% haze as measured based on the amount of scattering of transmittedlight. After 500 hours of exposure to 0.55 watts per square meter at 340nm from a xenon arc lamp in a chamber with a black panel temperature ofgreater than 80 C, a gray hazy precipitate formed gave the laminate ahaze level over 10%. A laminate was prepared with three polymer layersbetween two sheets of plain glass. The polymer layers were: 1) a UVbarrier layer containing Tinuvin® 326 in PVB that cutoff wavelengths oflight less than 390 nm; 2) a poly(ester-terephthalate) separator; and 3)a layer of the same type of thermochromic system as above. After thislaminate was exposed with the UV barrier facing the xenon arc lamp,almost no gray hazy precipitate formed in the TC layer, the haze levelwas less than 5% and the overall TC performance remained nearlyunchanged.

Separators and Pre-Lamination

Separator layers may be desirable in multilayer thermochromic systems toprevent intermixing of the thermochromic materials. It is particularlyuseful for the separator layer to have an index of refraction close tothat of the polymers used in the thermochromic layer so that reflectivelosses will be minimized. For example, poly(vinyl butyral) is an oftenused polymer for a LETC layer and it is reported to have an index ofrefraction from 1.485 to 1.490. When the LETC layer is contained in alayer of poly(vinyl butyral), plastic materials with good index ofrefraction match that may be used as chemical separators or diffusionbarrier layers between LETC layers may be selected from the followingTable: TABLE 5 Refractive Polymer Index Poly(4-methyl-1-pentene) 1.463Poly(vinyl propionate) 1.466 Poly(vinyl acetate) 1.467 Poly(vinyl methylether) 1.467 Poly(ethylene succinate) 1.474 Cellulose acetate butyrate1.475 Cellulose acetate 1.475 Ethylene/vinyl acetate copolymer-40% vinylacetate 1.476 Ethyl cellulose 1.479 Poly(methyl acrylate) 1.479Poly(oxymethylene) 1.480 Ethylene/vinyl acetate copolymer-33% vinylacetate 1.482 Poly(n-butyl methacrylate) 1.483 Ethylene/vinyl acetatecopolymer-28% vinyl acetate 1.485 Poly(methyl methacrylate) 1.489Polypropylene, isotactic 1.490 Methyl cellulose 1.497 Poly(vinylalcohol) 1.500 Poly(vinyl methyl ketone) 1.500 Poly(ethylene glycoldimethacrylate) 1.506 Poly(isobutylene) 1.510 Polyethylene, low density1.510Other, useful separators include polycarbonates, poly(esterterephthalates) and other polyesters, especially those polycarbonatesand polyesters that are hydrophobic or poor at solubilizing salts. Inaddition, crosslinked or highly crystalline materials may be used asseparators or diffusion barriers. For example poly(vinyl alcohol) isreasonably hydrophilic but in the absence of water it is a good barrierbecause of a high degree of order due to strong hydrogen bonding.Crosslinking in a separator in general may also be effective in theprevention of diffusion or migration of non-ionic ligands likepyridines, imidazoles and phosphines. Alternatively, non-ionic ligandsmay be attached to a polymer in the LETC layer or may be modified withthe attachment of polar or ionic substituents so they are less likely todiffuse through a separator. For example 1-hydroxyethybenzimidazole anda benzimidazole substituted with a quaternary ammonium group are lesslikely to diffuse through a hydrophobic, polymeric, separator layer thanan alkyl substituted benzimidazole like 1-EtBIMZ.

An alternative type of separator may be provided by a thermoset type ofadhesive that is used to bond multiple LETC layers together. Theadhesive forming system may contain reactive groups which optionallyform bonds directly to a polymer in the LETC layer. For example theadhesive may contain isocyanate groups which are part of a polyurethaneadhesive which covalently bond also to hydroxyl groups of a hydroxylgroup containing polymer on the surface of a LETC layer and make thesurface of the layer less permeable in the process. Other adhesivesystems include epoxies, silicones and acrylates.

When multi-layer thermochromic systems are used or when a separate UVbarrier layer is used to protect a thermochromic layer, it may bedesirable to prepare a pre-laminate. This pre-laminate may be preparedby an in-line process by co-extruding the thermochromic layer(s),optional barrier layer and the separator layer(s) at the same time, andthe layers may be bonded together while the polymer layers are still hotfrom the extruder dies. Alternatively, the layers may be extrudedtogether in a multi-manifold die to produce a barriers, TC layers andseparator in an intimately bonded stack.

A pre-laminate may also be prepared in an off-line process in which abarrier layer is bonded to one or more thermochromic layers with one ormore separator layers. Alternatively, two or more thermochromic layersmay be pre-laminated together with one or more separator layers in anoff line process. In the off line process, an advantage has beenrealized with the use of separator layers that have one or both of theirsurfaces pretreated, activated or excited to promote adhesion betweenthe separator layer and the UV barrier and/or thermochromic layers. Thepre-laminates made with pretreated, activated or excited surfaces on theseparator layer are easier to use in subsequent lamination betweensheets of glass or plastic since the layers stay together and behaveessentially as a single layer. Pretreating, activating or exciting thesurface dramatically decreases issues with de-lamination during years ofuse of LETC window panes. The separator surfaces may be pretreated,activated or excited by glow discharge, plasma or corona treatmentprocess in vacuum, inert atmosphere or in air. Alternately, pretreatmentwith ozone may be provided in an oxygen atmosphere.

Although, a separator or diffusion barrier layer is primarily used toprevent intermixing of the materials from individual thermochromiclayers when there are multiple thermochromic layers present, they mayalso act as barriers to UV light. This allows the separator to protectunderlying layers from UV exposure. Also, UV absorbing materials, likethose described in the additives section of this patent, may be morecompatible with the separator layer than a layer containing a LETCsystem. This is especially true given that some UV absorbers/stabilizerslike hydroxyphenylbenzotriazoles may have undesirable interactions withtransition metal ions. Also, the separator may contribute to thestructural integrity and shatter resistance of the window. In this casethe separator function may be provided by a relatively thick film orsheet of plastic. With multiple thermochromic layers and one or more,thick separator layers the overall window laminate may even becomehurricane, explosion, theft, vandalism and/or bullet resistant.

Seals

Seals are of interest especially for LETC layers which are sensitive tooxygen, water and/or environmental contaminants. For example, systemsinvolving iodide, systems involving phosphine compounds and systemsinvolving both iodide and phosphine compounds benefit from seals thatminimize the ingress of oxygen in the layers containing these systems.An edge seal may be provided when the LETC layer is laminated betweensheets of glass or sheets of plastic. The edge seal should cover theedge of the laminate around the entire perimeter to provide a barrierfor ingress of materials into the LETC layer. The edge seal may be athermoplastic, a thermoset, a rubber, a metallized tape or combinationsthereof. Useful thermoset seal materials are urethanes and epoxies.Suitable seals are epoxy systems disclosed for use as perimeter seals inU.S. Pat. No. 6,665,107, the contents of which are hereby incorporatedby reference. Useful thermoplastic seal materials are good barrierpolymers like poly(vinyl alcohol), poly(vinylidene chloride),(polyvinylidene fluoride), EVOH, and certain rubbers. Thermoplastic orthermoset systems overlayed with an impermeable metal foil or tape areuseful edge seal systems especially when the LETC systems containligands like iodide or phosphine compounds they are or are not used asligands.

Color and Color Coordinates

See “Principles of Color Technology, 2^(nd) Edition”, F. W. BillmeyerJr. and M. Saltzman, John Wiley and Sons, Inc. (1981) for a discussionof color and color coordinates including definitions of Y, L*, a*, b*and c*. The variation of c* with temperature is herein referred to asthe color sweep or shift of the LETC system. Generally, it is useful tohave small variations in c* i.e. small color sweep or shifts withtemperature. Many useful systems or combinations of systems have bothsmall c* values and small amount of color sweep as discussed below. Forthe use of LETC systems in applications like energy saving windows,especially, SRT™Windows, there is a demand for certain colors. Whilefixed tint windows which are gray, green, blue and bronze are inwidespread use, the most desirable color, (or lack thereof), forvariable tint windows is gray. This is especially true when the windowis or is able to become heavily tinted as the view through a heavilytinted gray window maintains the same color rendition for objects viewedthrough the window as is maintained with a lightly tinted or nearlycolorless window. Also it is highly desirable for the daylighting thatcomes in through the window to be color neutral so that people andobjects illuminated by that light have a normal appearance. Disclosedherein are interesting systems with a green, blue or bronze appearancewhen lightly tinted which change to gray when heavily tinted. Thesesystems and those that are close to gray at all tint levels areparticularly useful.

LETC systems with absorbance peaks throughout the visible and/or NIR aredisclosed herein. However, just a few special, single compositionsystems that are reasonably gray have been found. A few morecombinations of two compositions or layers of LETC materials have beendiscovered that provide good gray appearance throughout the entiretemperature range of intended use. Many more combinations involvingthree compositions or layers have been discovered that provide good grayappearance. Gray systems are illustrated in the Examples Section of thisdisclosure.

Useful LETC systems are those that not only maintain a consistent grayappearance throughout a large temperature range; they also have a largechange in visible light and/or total solar absorption. Single layer LETCsystems are disclosed herein, which have a c* of less than 25 throughoutthe temperature range of 25 C to 85 C and still have a change in Y fromgreater than 70 at 25 C to less than 15 at 85 C. Some of the two layerLETC systems have a c* of less than 21 throughout the temperature rangeof 25 to 85 C and still have a change in Y from greater than 75 at 25 Cto less than 15 at 85 C. Some of the three layer LETC systems have a c*of less than 15 and still have a change in Y from greater than 80 at 25C to less than 15 at 85 C. These systems have minimal color shift overthe active range of these novel TC systems.

Some of the multilayer systems have the added advantage that they alsoprovide reversibly variable transmission in the NIR as well as thevisible. However, the more compositions required the more complicatedand expensive the product becomes. Thus the systems that provide broadspectral attenuation and gray appearance with one or at most two layersare special.

Applications

A preferable use for our LETC layers is as part of an SRT™ windowpackage. Many configurations are possible for such windows. A fewconfigurations are:

-   -   1) A LETC layer that is laminated between sheets of tempered or        heat strengthened glass, wherein this laminate serves as the        center pane of a triple pane window. Preferably, in this        configuration, there is one or more than one low-e coating        between the LETC layer and the interior of the vehicle or        building in which the window is installed.    -   2) A LETC system is contained in a free standing plastic sheet        or is contained in a polymer layer which is laminated between        two plastic sheets and is used as the center pane of a triple        pane window. The interior pane of the triple pane window        preferably has a low-e coating on the surface facing the LETC        system.    -   3) A LETC layer is laminated between sheets of edge treated        glass and is used as the exterior pane of a double pane window.        Either one or both of the glass surfaces in contact with the gas        space of the double pane has a low-e coating.    -   4) A LETC layer is bonded to a sheet of tempered or heat        strengthened glass and a layer of plastic film is bonded to the        LETC layer. This pane is used as the exterior pane of a double        pane window with the plastic film in contact with the gas space        or this pane is used as the center pane of a triple pane window.        A pane with a low-e layer is used as the interior pane in either        case and the low-e layer is oriented to face the pane with the        LETC layer.    -   5) A LETC layer is laminated between a sheet of NIR absorbing        glass and the uncoated side of a sheet of glass coated with a        low emissivity coating, which coating has substantial NIR        absorption character. This laminate is used as the exterior pane        of a double pane window with the low emissivity coating in        contact with the gas space of the double pane window.    -   6) A LETC layer that is laminated between a first sheet of        tempered or heat strengthened glass and the uncoated side of a        second sheet of tempered or heat strengthened glass coated with        a hard coat low emissivity coating. This laminate is used as the        interior pane of a double pane window, wherein the hard coat low        emissivity coating is in contact with the interior of the        vehicle or building in which the window is installed.        Many more examples are given in our co-pending application on        window structures.

SRT™ windows may be used in a variety of applications such as variablelight absorption windows for residential and commercial buildingsincluding skylights and atrium glazing and variable light absorptionwindows for boats, ships, aircraft and motor vehicles including moonroofs and sun roofs. The windows may include artful designs of differentcolored LETC systems like a variable light transmission stained glasswindow.

When a triple pane window is constructed with the LETC system as part ofthe center pane, there are two interfaces in contact with a gas for eachpane, giving a total of six interfaces. The reflection from each ofthese interfaces will add up and may become objectionable. Thus we havediscovered an advantage to placing anti-reflection coating on one ormore surfaces in the window package.

LETC systems may be used to prepare variable reflectance mirrors byplacing LETC layer on a reflector or on a substrate coated with areflector. The LETC layer may be protected by laminating the layerbetween a transparent substrate and a reflector coated substrate. Thereflector may be used as a resistive heater to heat the LETC layer andthus vary the reflectance of the mirrors.

LETC systems may be used as a means to monitor the temperature invarious environments as long as the transmission change of the systemcan be measured or observed. Temperature determination may range fromvisual comparisons to full spectral measurements. This is a particularlyuseful means of monitoring temperature at the tip of a fiber optic cablethat may be used for, among other things, as a catheter for insertioninto a body.

An SRT™ window may be used to monitor the intensity and directness ofsunlight, as both the transmission and the temperature of thethermochromic layer change with sunlight intensity in a reproduciblemanner.

LETC systems may be used to display information in devices where certainregions are heated or the active LETC layer is patterned in a mannersuch that individual segments may be heated. Heating may be provided byresistive heating or by selective light exposure by a light source suchas a laser or other source providing a focused light beam or localizedheating.

While our best understanding of these TC processes involves changes inconcentrations of MLC's, we have discovered and herein describe manythermochromic systems that have a reversible, net increase in theirabilities to absorb light energy in the visible and/or NIR range as thetemperature of the system is increased, no matter what the explanation.

EXAMPLES

Table 6 gives the formulations of liquid solution LETC systems forExamples 1-46. In each case, the solution was prepared by dissolving thematerials in 5 milliliters of γ-BL. In each example, some of thesolution was placed in a 1 cm borosilicate cuvette, a small stir bar wasplaced in the cuvette and the cuvette was placed in the sample beam of aShimadzu UV-3101PC spectrophotometer. The solution was stirred andheated and the temperature was monitored with a thermocouple immersed inthe solution in the cuvette. A similar, unheated 1 cm cuvette containingonly the solvent was placed in the reference beam of thespectrophotometer. In each example the absorption spectrum of thesolution was measured from 350 nm to 1150 nm at 25 C and then thesolution was heated to 45 C and the spectrum was measured. Then thesolution was heated to 65 C and the spectrum was measured and so on at85 C and 105 C. FIGS. 1-46 correspond, numerically, to Examples 1-46.The Figures show the spectrum measured at 25 C, at 45 C, at 65 C, at 85C and at 105 C for the solutions described in these Examples. In eachcase the spectrum with the lowest absorbance corresponds to 25 C, thenext highest absorbance spectrum corresponds to 45 C and so on such thatthe spectrum with highest absorbance peaks in each Figure correspondsthat measured at 105 C. In all the FIGS. 1-46, the x axis, (horizontalaxis), gives the wavelengths in nanometers and the y axis, (verticalaxis), gives the absorbance values. For the examples in Table 6, themolarity values were calculated based on an assumed 5 ml total solutionvolume. Volume changes due to components dissolved in the 5 ml of γ-BLwere not considered. TABLE 6 Conc. Type Materials in LETC System(molarity) Example 1 - FIG. 1 HεL TBABr 0.21 LεL TMOLP 0.19 MetalNi(ClO₄)₂—6H₂O 0.02 Example 2 - FIG. 2 HεL TEACl—H₂O 0.2 LεL TMOLP 0.51Metal Ni(ClO₄)₂—6H₂O 0.02 Example 3 - FIG. 3 HεL TBAI 0.2 LεL TMOLP0.022 Metal Co(BF₄)₂—6H₂O 0.002 Metal Ni(ClO₄)₂—6H₂O 0.002 Example 4 -FIG. 4 HεL TBAI 0.15 HεL CF₃COOLi 0.35 LεL TMOLP 0.16 MetalCo(BF₄)₂—6H₂O 0.01 Example 5 - FIG. 5 HεL TBABr 0.12 HεL2,2′-ethane-1,2-diyldipyridine 0.04 LεL NPG 2.05 Metal Ni(ClO₄)₂—6H₂O0.04 Example 6 - FIG. 6 HεL LiBr 0.05 HεL Ph₃P 0.2 LεL TMOLP 1.27 MetalCo(BF₄)₂—6H₂O 0.01 Example 7 - FIG. 7 HεL TEACl—H₂O 0.16 HεL Ph₃P 0.2LεL EG 1.9 Metal Ni(NO₃)₂—6H₂O 0.02 Example 8 - FIG. 8 HεL TBABr 0.06HεL N-Bu-di(1-MeBIMZ-2-yl-methyl)amine 0.02 LεL TMOLP 0.095 MetalNi(ClO₄)₂—6H₂O 0.02 Example 9 - FIG. 9 HεL TBAI 0.02 HεL Ph₃P 0.1 LεLTMOLP 0.35 Metal Co(BF₄)₂—6H₂O 0.002 Example 10 - FIG. 10 EXM ZnCl₂ 0.3HεL TEACl—H₂O 0.2 LεL Glycerol 0.013 Metal Cu(NO₃)₂—2.5H₂O 0.0025 MetalCo(BF₄)₂—6H₂O 0.012 Example 11 - FIG. 11 EXM ZnCl₂ 0.32 HεL TEACl—H2O(TEACl) 0.09 Metal Cu(NO₃)₂—2.5H₂O 0.01 Example 12 - FIG. 12 HεL TTCTD0.02 LεL 2-methyl-1,3-propanediol 0.38 Metal Ni(ClO₄)₂—6H2O 0.01 Example13 - FIG. 13 HεL TBABr 0.1 HεL 2,2′-propane-2,2-diylbis(1-propyl-1H-0.04 benzimazole) LεL TMOLP 0.18 Metal Ni(ClO₄)₂—6H₂O 0.02 Example 14 -FIG. 14 HεL LiBr 0.2 LεL NPG 0.86 Metal Ni(NO₃)₂—6H₂O 0.021 Example 15 -FIG. 15 HεL Ph₃P 0.3 LεL NPG 1.23 Complex NiBr₂(Ph₃P)₂ 0.01 Example 16 -FIG. 16 HεL Ph₃P 0.044 HεL LiBr 0.16 LεL EG 1.3 Metal Ni(NO₃)₂—6H₂O 0.02Example 17 - FIG. 17 HεL N-propyl-N-pyridin-2-ylpyridin-2-amine 0.015HεL LiBr 0.2 HεL 4-tert-butylpyridine 0.01 LεL TMOLP 0.29 MetalNi(ClO₄)₂—6H₂O 0.02 Example 18 - FIG. 18 HεL LiBr 0.2 HεLN-propyl-N-pyridin-2-ylpyridin-2-amine 0.025 LεL TMOLP 0.15 MetalNi(ClO₄)₂—6H₂O 0.04 Example 19 - FIG. 19 HεL TBABr 0.04 LεL NPG 1.33Complex NiBr₂[2,2′-propane-2,2-diylbis(1-pentyl-1H- 0.04benzimidazole)]₂ Solvent γ-GB Example 20 - FIG. 20 HεL TBA(4-MeOPh)₂PO₂0.05 LεL TMOLP 1.51 LεL Di-TMOLP 0.17 Metal Co(BF₄)₂—6H₂O 0.01 Example21 - FIG. 21 HεL TBABr 0.015 HεL 2-mercapto-5-methylbenzimidazole 0.005LεL TMOLP 0.031 Metal Ni(ClO₄)₂—6H₂O 0.005 Example 22 - FIG. 22 HεLpoly(2-vinylpyridine) 0.12 HεL LiBr 0.2 LεL EG 0.95 Metal Ni(NO₃)₂—6H₂O0.02 Example 23 - FIG. 23 HεL TBABr 0.08 HεL2-mercapto-1-methylimidazole 0.1 LεL TMOLP 0.31 Metal Ni(ClO₄)₂—6H₂O0.02 Example 24 - FIG. 24 HεL TBABr 0.08 LεL TMOLP 0.95 MetalCo(BF₄)₂—6H₂O 0.005 Example 25 - FIG. 25 HεL choline chloride 0.1 LεLTMOLP 2.34 Metal Co(BF₄)₂—6H₂O 0.01 Example 26 - FIG. 26 HεL TBABr 0.06HεL 1-Et-BIMZ 0.0602 LεL NPG 1.54 Metal Ni(ClO₄)₂—6H₂O 0.02 Example 27 -FIG. 27 HεL TBAI 0.04 LεL TMOLP 0.07 Complex NiI₂(Ph₃P)₂ 0.005 Example28 - FIG. 28 HεL TBABr 0.08 HεL 2,2′-propane-2,2-diyl(1H-benzothiazole)0.04 LεL TMOLP 0.064 Metal Ni(ClO₄)₂—6H₂O 0.02 Example 29 - FIG. 29 HεL6-methyl-2,2′-dipyridyl 0.02 HεL LiBr 0.16 LεL TMOLP 0.23 MetalNi(ClO₄)₂—6H₂O 0.02 Example 30 - FIG. 30 HεL6,6′-dimethyl-2,2′-dipyridyl 0.02 HεL LiBr 0.2 LεL TMOLP 1.21 MetalNi(ClO₄)₂—6H₂O 0.02 Example 31 - FIG. 31 HεL TBAI 0.2 HεL LiBr 0.04 LεLEG 0.3 Metal Ni(NO₃)₂—6H₂O 0.02 R/O Oxford Blue 0.0037 Example 32 - FIG.32 HεL CF₃COOLi 0.35 HεL TEAI 0.15 LεL EG 0.6 Metal Co(BF₄)₂—6H₂O 0.01R/O Ruby Red 0.0025 Example 33 - FIG. 33 HεL TBABr 0.061 HεLDi-(2-picolyl)amine 0.024 LεL TMOLP 0.066 Metal Ni(ClO₄)₂—6H₂O 0.02Example 34 - FIG. 34 LεL N-propyl-N-pyridin-2-ylpyridin-2-amine 0.27Complex Ni(diisobutyldithiophosphinate)₂ 0.02 Example 35 - FIG. 35 HεLPh₃P 0.06 HεL TBAI 0.06 HεL CF₃COOLi 0.35 LεL NPG 0.5 MetalCo(BF₄)₂—6H₂O 0.02 Example 36 - FIG. 36 HεL TBABr 0.1 HεL6-methyl-N-phenyl-N-pyridin-2-ylpyridin- 0.02 2-amine LεL NPG 1.52 MetalNi(ClO₄)₂—6H₂O 0.02 Example 37 - FIG. 37 HεL TBABr 0.1 HεL1-ethyl-N-methyl-N-pyridin-2-yl-1H- 0.02 benzimidazol-2-amine LεL NPG0.47 Metal Ni(ClO₄)₂—6H₂O 0.02 Example 38 - FIG. 38 HεL TBABr 0.1 HεLN-[(1-methyl-1H-benzimidazol-2-yl)methyl]-N- 0.02pyridin-2ylpyridin-2-amine LεL NPG 0.61 Metal Ni(ClO₄)₂—6H₂O 0.02Example 39 - FIG. 39 HεL TBABr 0.1 HεLN,N,N′,N′-tetramethyl-1,3-propanediamine 0.02 LεL NPG 1.85 MetalNi(ClO₄)₂—6H₂O 0.02 Example 40 - FIG. 40 HεL TBABr 0.1 HεLN-pyridin-2-ylpyridin-2-amine 0.008 HεLN-ethyl-N-(pyridine-2ylmethyl)pyridin-2-amine 0.005 LεL NPG 0.59 MetalNi(ClO₄)₂—6H₂O 0.02 Example 41 - FIG. 41 HεL TBABr 0.2 HεLN-pyridin-2-yl-N-(pyridin-2-ylmethyl)pyridin-2- 0.04 amine LεL NPG 0.089Metal Ni(ClO₄)₂—6H₂O 0.02 Example 42 - FIG. 42 HεL TBAI 0.009 HεL4-(3-PhPr)Pyr 0.003 LεL TMOLP 0.014 Metal (TBA)₂NiI₄ 0.003 Additive Ph₃P0.001 Additive Tinuvin ® 405 0.003 Example 43 - FIG. 43 HεL TBABr 0.1HεL 2-pyridin-2-ylethanamine 0.02 LεL NPG 0.74 Metal Ni(ClO₄)₂—6H₂O 0.02Example 44 - FIG. 44 HεL TBABr 0.1 HεL6-methyl-N-[(6-methylpyridin-2-yl)methyl]-N- 0.02pyridin-2-ylpyridin-2-amine LεL NPG 1.21 Metal Ni(ClO₄)₂—6H₂O 0.02Example 45 - FIG. 45 HεL TBABr 0.1 HεLN-(6-methylpyridin-2-ylmethyl)pyridin-2-amine 0.02 LεL NPG 1.49 MetalNi(ClO₄)₂—6H₂O 0.02 Example 46 - FIG. 46 HεL potassium hydrotris(3,5-0.005 dimethylpyrazol-1-yl)borate HεL TBABr 0.026 LεL TMOLP 0.026 MetalNi(ClO₄)₂—6H₂O 0.005

Examples of Gray Combinations

Some of the single layer LETC systems we have discovered, which have ac* of less than 25 throughout the range of 25 C to 85 C with a Y fromgreater than 70 at 25 C and less than 15 at 85 C are listed in Table 7.These are c* and Y values for the LETC system alone and not for othercomponents like substrates that might be part of a window package. Eachexample in Table 7 is based on a formulation given by the entry fromTable 27. The spectra used to calculate c* and Y is the given percentageof the spectra obtained when heating a solution of the formulation givenin Table 27. LETC systems with the characteristic given in Table 7 canbe achieved either by using the percentage of the formulation from Table27 or by keeping the formulation the same and changing the path lengthor layer thickness of the system. It is also possible to achieve similarresults with these systems for a wide variety of concentrations and pathlengths. Thus information from liquid solution based LETC systems withlarge path lengths can be used to design thinner polymer layer basedsystems with similar change in white light transmission, similar colorsand similar color sweep or shift with temperature. TABLE 7 % of Entry 25C. 45 C. 65 C. 85 C. Example # of Table 27 Y|a*|b*|c* Y|a*|b*|c*Y|a*|b*|c* Y|a*|b*|c* 47 80% of 925 75.6|−10.6|−4.7|11.660.0|−2.9|−2.0|3.5 33.9|11.9|−2.2|12.1 14.9|22.3|−7.2|23.4 48 105% of708  74.8|−18.3|−4.6|18.8 61.6|−15.9|−8.2|17.9 36.4|−9.3|−14.4|17.214.9|−0.1|−16.0|16.0 49 89% of 733 72.3|−18.3|1.4|18.459.2|−14.1|4.4|14.8 34.8|−4.3|5.9|7.3 14.7|4.8|3.9|6.2 50 82% of 82773.2|−10.4|−6.4|12.3 57.0|−9.0|−7.6|11.8 32.8|−3.9|−9.1|9.914.7|4.4|−4.0|5.9 51 78% of 830 75.4|−9.3|−4.7|10.4 56.7|−7.8|−6.8|10.430.9|−4.0|−9.9|10.7 14.8|−1.5|−3.6|3.9 52 80% of 829 76.1|−7.7|−3.6|8.556.4|−4.1|−9.2|10.0 31.1|3.1|−16.9|17.1 14.9|9.1|−15.8|18.2

For examples of two layer systems, the spectra in FIGS. 1-32, werecombined in various combinations and each combination was checked to seeif it met certain performance criteria with regard to color and range oftransmission. Combinations made by adding various amounts of the spectrafrom just two LETC layers are given below. These combinations met thecriteria of c* less than 20 throughout the range of 25 C to 85 C with aY from greater than 75 at 25 C and less than 15 at 85 C. These arevalues for the LETC system alone and not for other components likesubstrates that might be part of a window package. In practice one canreliably predict the combined spectrum of two or more systems by simplyadding the spectra of two separate systems at each temperature ofinterest. Since the TC systems are, or would, be in separate layers, itis not surprising that the absorption spectra of light passing throughthe layers would be a simple sum of the separate absorption spectra.From the summed absorption spectra one can calculate the overall whitelight transmittance, Y, and the color coordinates, (see Principles ofColor Technology, 2nd Edition”, F. W. Billmeyer Jr. and M. Saltzman,John Wiley and Sons, Inc. (1981)). TABLE 8 % of % of 25 C. 45 C. 65 C.85 C. Ex. # Figure Figure Y|a*|b*|c* Y|a*|b*|c* Y|a*|b*|c* Y|a*|b*|c* 5366% of 2 86% of 12 87.3|−1.0|3.1|3.3 70.0|5.9|5.3|7.9 38.3|11.5|3.2|12.014.7|14.0|−2.8|14.3 54 32% of 3 56% of 20 89.6|−4.7|9.6|10.772.8|−6.6|2.5|7.1 38.3|−4.4|−11.6|12.4 14.7|5.5|−13.7|14.8 55 60% of 454% of 12 84.3|−1.2|8.0|8.0 65.0|1.2|3.9|4.1 35.4|5.6|−4.3|7.014.8|10.5|−10.6|14.9 56 24% of 5 28% of 27 91.2|−4.5|5.5|7.170.8|−2.4|6.4|6.9 37.4|5.1|2.2|5.6 14.6|13.8|−0.2|13.8 57 28% of 5 16%of 31 88.8|−7.5|8.8|11.5 69.2|−8.2|11.4|14.0 36.9|−5.8|13.7|14.914.5|4.0|10.2|11.0 58 34% of 5 62% of 33 78.8|−7.8|6.2|10.060.8|−10.9|9.8|14.6 33.0|−8.8|0.8|8.9 15.0|−3.1|−12.7|13.1 59 36% of 510% of 23 90.7|−8.5|8.4|11.9 69.1|−10.1|9.6|14.0 35.7|−10.3|4.8|11.414.7|−4.0|−9.7|10.4 60 38% of 5 34% of 9  90.4|−8.0|8.6|11.868.5|−8.9|8.3|12.2 35.3|−5.7|−3.0|6.4 14.8|−0.9|−14.2|14.3

For examples of three layer systems, the spectra in FIGS. 1-46, werecombined in various combinations and the combinations were checked tosee if they met certain performance criteria with regard to color andrange of transmission. Many combinations gave good values for Y and c*when adding various amounts of the spectra from three LETC layers. Somerepresentative results made are given below. These combinations met thecriteria of c* less than 10 throughout the range of 25 C to 85 C with aY from greater than 80 at 25 C and less than 15 at 85 C. These arevalues for the LETC system alone and not for other components likesubstrates that might be part of window package. TABLE 9 % of % of % of25 C. 45 C. 65 C. 85 C. Ex. # Figure Figure Figure Y|a*|b*|c* Y|a*|b*|c*Y|a*|b*|c* Y|a*|b*|c* 61 10% of 1 25% of 5  30% of 27 90.2|−5.3|5.9|7.968.7|−3.6|6.6|7.6 34.5|2.7|1.8|3.3 12.4|9.6|−1.2|9.7 62 10% of 1 20% of26 35% of 27 89.8|−2.3|−0.5|2.3 66.7|0.2|−4.3|4.3 33.2|4|−8|8.914.2|7.5|−0.1|7.5 63 15% of 1 100% of 6  95% of 12 80.3|−2.2|3.7|4.359.8|−2.8|1.9|3.4 32.5|3|1.8|3.5 14.1|9.3|3.2|9.8 64 20% of 1 35% of 4 60% of 36 85.6|−4.2|8|9 63.9|0|7|7 32.1|6.9|2.4|7.3 14.7|8.4|−4.7|9.6 6525% of 1 65% of 2  80% of 12 86.4|−2.7|3.3|4.3 69.1|2.4|4.6|5.237.7|5.7|1.2|5.8 14.5|8.2|−5.5|9.9 66 25% of 1 30% of 36 60% of 4182.6|−0.7|−1.8|2 66.9|−0.1|−0.5|0.5 36|3.1|−1.7|3.5 14.6|6.2|−7.7|9.9 6730% of 1 65% of 44 40% of 46 81.5|−6.8|4.9|8.4 58.2|−4.3|8.7|9.728.5|2.5|9|9.3 14.3|6.2|6.8|9.2 68 35% of 1 30% of 12 65% of 4181.6|0.5|−3.4|3.5 67.6|0.5|−2.7|2.7 37.9|2.2|−3.4|4.1 14.4|6.9|−7.2|1069 45% of 1 15% of 23 85% of 39 82.2|−2.8|1.5|3.2 63.8|0.8|1.7|1.836.4|1.8|7.8|8 14.8|8.6|0.4|8.6 70 45% of 1 50% of 39 50% of 4584.6|−4.9|3.9|6.3 65|−1.8|7.2|7.4 35.1|3|9.4|9.9 14.3|7.1|4.9|8.7 71 50%of 1 90% of 12 100% of 24  82.8|0.5|3.3|3.3 63.3|2.4|3.2|434.2|4.7|2.2|5.2 14.7|9.1|3|9.6 72 55% of 1 15% of 7  65% of 3686.1|−6.9|5.1|8.6 63.7|−2.4|5|5.5 31.4|5.8|1.6|6 14.7|8.5|−4|9.5 73 55%of 1 60% of 9  90% of 39 81|−2.3|1.9|3 62.5|1.9|0.8|2 35.8|5.8|0.5|5.814.7|9.2|0.3|9.2 74 55% of 1 30% of 14 70% of 36 87.4|−6.8|6.7|9.566|−1.8|9.6|9.8 33.1|4.2|8.7|9.7 14.8|3.1|2|3.7 75 95% of 1 15% of 1365% of 36 83.4|−6.6|5.3|8.5 62.2|−0.7|6.6|6.6 31|8|5.6|9.714.5|9.4|1.3|9.5 76 95% of 1 10% of 28 65% of 36 82.1|−5.4|3.8|6.660.8|0.5|4|4.1 31|8.3|2.7|8.7 15|9.3|−1.4|9.4 77 95% of 1  5% of 32 65%of 36 81.7|−5|5.6|7.5 60.3|−0.5|7.1|7.1 30.7|5.7|6.5|8.714.8|6.3|2.8|6.9 78 95% of 1 65% of 36 15% of 37 82.7|−7.8|5.3|9.461.7|−2.1|6.6|6.9 30.7|6.9|5.2|8.6 14|9.6|0.1|9.6 79 100% of 1   5% of19 70% of 36 84.7|−7.9|6.1|9.9 63.4|−2.5|7.9|8.3 32|5.9|7.7|9.714.9|7.6|3.7|8.4 80 20% of 2 65% of 37 30% of 45 80.4|−5.9|4.2|7.364.2|−2.3|7.5|7.9 34.5|4.8|7.5|8.9 14.8|9.4|3|9.9 81 25% of 2 15% of 2385% of 39 83.6|−1.5|1.5|2.1 65.3|2.8|1.9|3.4 37|3|7.4|8 14.6|8.7|−2|8.982 25% of 2 35% of 36 50% of 41 84.1|−1|−0.6|1.2 67.9|0.3|0.8|0.835.9|2.4|−1.5|2.8 14.5|3.6|−9.1|9.8 83 25% of 2 55% of 39 45% of 4585.6|−3.1|3.3|4.5 66.2|1.1|5.6|5.7 35.6|5.7|5.6|8 14.1|9.1|−1.3|9.2 8430% of 2 60% of 9  90% of 39 82.6|−0.6|2|2.1 64.3|4.4|1.1|4.536.5|7.6|−0.2|7.6 14.5|9.7|−2.2|9.9 85 30% of 2 45% of 18 20% of 2781.8|−7.9|−1|8 66.4|−4.8|3|5.6 37|0|6.4|6.4 14.4|3.2|7.9|8.5 86 30% of 225% of 27 50% of 37 83.2|−3.8|2.8|4.7 67.9|−0.6|4.4|4.4 37.6|4.9|3.8|6.215|8.9|3.3|9.5 87 35% of 2 10% of 7  70% of 36 87.8|−5|5.4|7.465.5|0.9|6.7|6.7 31.8|8.2|3.6|8.9 14|8.5|−3.5|9.2 88 35% of 2 35% of 1245% of 44 86.4|−4.4|5.2|6.8 64.2|−1.9|9.5|9.7 32.5|0.7|9.9|1014.6|2.2|6.3|6.7 89 35% of 2 75% of 12 30% of 16 87.1|−5.3|4.9|7.268.7|−3.5|8.2|8.9 37.2|−2.9|9.5|10 14.5|−1.7|8|8.1 90 45% of 2 15% of 3140% of 43 83|−5.4|3.2|6.2 64.4|0.4|3.8|3.8 34.8|2.9|7.7|8.314.7|3.9|7.9|8.8 91 45% of 2 10% of 32 55% of 36 81.6|0.5|5.4|5.460.7|5.2|6.8|8.6 31|7.4|3.8|8.3 14.5|4.1|−2.9|5.1 92 45% of 2 35% of 3640% of 40 83.4|−6.1|6.4|8.9 61|1.1|9.9|9.9 30.6|4.2|6.9|8.114.6|−0.7|−2.1|2.2 93 50% of 2 10% of 13 65% of 36 87.3|−4|5.3|6.766.8|2.2|7.4|7.7 33.3|8|4.8|9.4 14.8|6.1|−2.7|6.7 94 50% of 2 10% of 1965% of 36 87.9|−5|6.3|8 67.2|1.3|8.5|8.6 33.5|7.4|5.9|9.514.4|6.4|−2|6.7 95 70% of 2 80% of 12  5% of 45 87.2|−1.8|3.6|469.7|3.9|6.6|7.6 37.6|7|6.2|9.4 14.2|7.8|1.8|8 96 75% of 2 5% of 9 80%of 12 87.3|−1.9|3.6|4 70.2|3.4|6|6.9 38.4|5.9|4|7.2 14.6|6.9|−1.6|7.1 9775% of 2  5% of 11 80% of 12 86.8|−2.8|4.7|5.5 69.8|2.6|7.4|7.938.1|5.7|4.7|7.4 14.5|7.5|−2.3|7.9 98 80% of 2 70% of 12  5% of 3186.7|−3.1|4.5|5.4 69.9|0.2|7.7|7.7 37.9|−1.1|9.6|9.7 14.1|−0.8|5|5.1 9910% of 3 35% of 12 80% of 17 80.2|−7.7|−2.3|8 66|−7.9|−2.1|8.237.3|−4.2|−4.1|5.8 14|6.3|−4.1|7.5 100 10% of 3 70% of 13 40% of 1681.4|−6.7|7.2|9.8 63.8|−5.6|5.5|7.8 33.1|−1.3|−0.7|1.514.5|−0.7|−5.1|5.2 101 15% of 3 50% of 9  30% of 26 89|−6.9|4.7|8.365.2|−7.1|−0.2|7.1 32|−5.6|−5.7|8 14.9|−1.8|3.7|4.1 102 15% of 3 50% of20 30% of 45 89.3|−3.9|7.7|8.7 70.2|−7|6.4|9.5 35.5|−9.8|0.2|9.814.2|−6.1|−2.3|6.5 103 25% of 3 65% of 13 100% of 24  80.3|−1.6|9.5|9.763.6|−0.5|5.4|5.5 33.3|3.7|−1.7|4.1 14.8|6.9|0.2|6.9 104 25% of 3 55% of20  5% of 31 88.9|−4.2|9|9.9 72|−7.1|3.7|8 37.9|−8.6|−5|9.914.6|−0.3|−4.9|4.9 105 30% of 3 65% of 14 35% of 28 80.7|−2.7|7.2|7.764.3|1.2|3.8|4 36.3|2.9|−2.5|3.8 14.4|1.8|−4.7|5 106 45% of 3 50% of 2525% of 28 80|−3.7|8.4|9.2 61.8|−6.7|1.6|6.9 33.8|−5|−2.2|5.514.4|5|8.3|9.7 107 10% of 4 20% of 5  30% of 27 90.2|−4.2|6.2|7.569.9|−3|6.8|7.4 36.8|2.1|3.3|3.9 14.1|8.6|1.7|8.8 108 10% of 4 10% of 2260% of 44 84.2|−7.3|6.7|9.9 58.9|−7.7|6.4|10 28.7|−5.8|0.2|5.814.9|−3.9|−7.1|8.1 109 25% of 4 30% of 36 40% of 44 85.2|−4.9|7.9|9.360.7|−2.5|9.4|9.8 29.1|3|6.3|7 13.8|5.3|0.1|5.3 110 25% of 4 50% of 3735% of 45 80.6|−5.6|6.8|8.8 62.6|−3.9|9.1|9.9 32.8|1.5|8.4|8.513.8|6|4.1|7.2 111 25% of 4 40% of 39 45% of 45 85.2|−3.3|6.1|6.965.4|−1.1|7.6|7.7 35.4|2.9|7.4|7.9 14.9|7|1.9|7.2 112 30% of 4 60% of 9 75% of 39 81.8|−0.7|5.2|5.3 62.6|2|3.5|4 35.4|4.3|2.2|4.8 15|7.2|2|7.5113 30% of 4 20% of 10 55% of 36 81.7|−1.8|8.5|8.7 60.7|0.7|9.2|9.230.8|6.4|7.2|9.6 14.2|7.2|3.6|8.1 114 30% of 4 15% of 12 55% of 4080.1|−4.7|8.1|9.3 57.3|2.6|9.3|9.7 29.8|7.7|4.9|9.1 15|5.5|−3.4|6.5 11530% of 4 55% of 13 30% of 45 81.7|−1.6|7.1|7.3 62.6|1.5|7.9|831.9|6.5|7|9.6 14.3|5.5|4.8|7.3 116 35% of 4 55% of 36 20% of 4284.7|−4.8|8.3|9.6 64.1|−0.8|9|9 32.7|6.1|7|9.3 14.9|7.6|2.5|8 117 40% of4 40% of 9  45% of 43 81.1|−3.6|5.4|6.4 59.9|2.3|2.2|3.231.7|9.2|−3.2|9.7 14.9|9.3|−3|9.7 118 40% of 4 50% of 12 25% of 3580.3|1.7|9.5|9.7 62.4|3.4|8.5|9.1 34.4|5.8|6.5|8.7 14.1|8.1|4.3|9.2 11940% of 4 35% of 18 20% of 45 80.5|−8.2|4.4|9.3 63|−8.4|5.3|9.934.5|−7.1|4.1|8.2 14.8|−4.8|0.3|4.8 120 40% of 4 30% of 19 25% of 2786.2|−3.6|9.2|9.9 67.9|−2.4|8.1|8.4 36.7|0.8|5.8|5.9 14.1|4.5|6.1|7.6121 55% of 4 10% of 8  55% of 12 83.1|−1.8|8.5|8.7 64|0.6|8.1|8.134.9|5|4.8|6.9 14.8|9.5|1.4|9.6 122 55% of 4 50% of 12  5% of 3184.2|−1.7|8.6|8.8 65.2|−0.1|7.1|7.1 35.6|2.2|6.1|6.5 14.7|6.4|4.6|7.9123 55% of 4 55% of 12 20% of 33 80.9|−1.4|7.6|7.7 62.6|0|7.2|7.234.5|3.4|4|5.3 14.7|7.4|1.2|7.5 124 60% of 4 10% of 9  55% of 1284|−1.3|8.7|8.8 64.5|0.5|6.3|6.3 34.7|3.5|1.5|3.8 14.3|6.5|−1|6.6 12560% of 4 50% of 12  5% of 23 84.3|−2|9.1|9.3 65|−1.7|8.2|8.435.3|−2.4|8.3|8.7 14.7|0.1|4.8|4.8 126 10% of 5 10% of 12 55% of 4486.9|−5.8|6.3|8.6 62|−3.7|9.2|9.9 30.2|2.7|5.6|6.2 14.3|8.4|−1.5|8.5 12710% of 5 55% of 12 35% of 16 88.3|−6.8|5.8|8.9 68.5|−5.7|7.7|9.636.8|−1.9|5.6|5.9 14.9|3.8|1.2|4 128 15% of 5 20% of 25 35% of 2790.4|−3|4.1|5.1 70.2|−5.6|5|7.5 37.4|−6.3|4.4|7.7 14.8|−0.3|7|7 129 15%of 5  5% of 27 45% of 44 88|−6.3|6.4|9 63.7|−5.2|8.1|9.6 31.4|0|2.1|2.114.5|5.2|−6.9|8.7 130 15% of 5 20% of 28 45% of 45 83.8|−2.4|4.2|4.862.6|0.7|7.4|7.5 32.6|5.6|7.8|9.6 14.3|7.7|4.1|8.8 131 20% of 5 10% of6  35% of 27 90.4|−4.2|5.5|6.9 69.9|−3.7|7.3|8.2 36.3|0.7|6.2|6.213.4|7.3|6.5|9.8 132 20% of 5 30% of 9  35% of 18 83.6|−9.4|3.3|1065|−7.2|6.5|9.6 34.7|0.9|4.4|4.5 14.2|8.4|0.7|8.4 133 25% of 5 10% of 2815% of 31 85.5|−4.9|6.6|8.3 65.5|−4|7.7|8.7 34.9|−1.3|9.3|9.414.1|6.6|6.5|9.3 134 25% of 5 10% of 31 10% of 32 82.1|−1.6|7.6|7.761|−0.9|7.6|7.6 32.1|0.6|4.1|4.2 13.6|7.2|−2.8|7.8 135 30% of 5 15% of9  15% of 27 91|−6|6.9|9.1 70.1|−5.3|7.1|8.9 36.8|0.1|−0.4|0.414.9|6.5|−6.9|9.4 136 30% of 6 30% of 14 75% of 36 87.3|−4.9|7|8.664.8|−1.7|9.5|9.7 31.8|3.3|9.1|9.7 14.3|2.5|3.5|4.3 137 30% of 6 25% of27 55% of 37 80.9|−3.7|2.8|4.6 64.5|−2.9|3.1|4.2 35.5|2.5|3|3.914.7|8.7|4.9|9.9 138 35% of 6 15% of 16 75% of 36 86.1|−6.1|6.7|963.2|−4.4|8.9|9.9 31.2|0.8|9.5|9.5 14.8|1.7|6.5|6.7 139 35% of 6 35% of18 45% of 36 80.3|−7.4|1.3|7.5 60.5|−3.4|3.2|4.7 31.5|5.1|4.2|6.614.6|9.5|2|9.7 140 50% of 6 75% of 36 10% of 39 84.6|−3.7|5.4|6.561.5|−0.5|5.7|5.7 30.4|6.9|5.4|8.8 14.5|9.7|2.2|9.9 141 55% of 6  5% of34 75% of 36 82.4|−5.3|7.8|9.4 59.8|−3.3|8.4|9 30.1|3|8.5|9 15|5|6.3|8.1142 55% of 6 70% of 36 10% of 43 83.9|−4.2|5|6.6 60.5|−0.9|4.7|4.829.8|6.7|3.6|7.6 14.5|9.2|0.8|9.2 143 65% of 6 85% of 12 20% of 1683.1|−3.9|4.6|6 63|−5.6|5.3|7.7 34.2|−3.6|7.5|8.4 14.4|0.9|9.9|10 14480% of 6 75% of 12 20% of 40 80.1|−2.5|4.5|5.1 58.5|−1.1|4.7|4.831.3|4|5.1|6.4 14.3|8.3|5.2|9.8 145 85% of 6 10% of 7  80% of 1282.1|−2.5|3.2|4.1 61.6|−3.9|0|3.9 33.5|1|−3.5|3.6 14.6|8.5|−4.9|9.8 146100% of 6   5% of 10 90% of 12 80|−1.2|3.8|4 59.9|−2.6|2.1|3.433.1|2.5|1.9|3.1 14.6|8.8|3|9.3 147 100% of 6  85% of 12  5% of 2081.4|−1.5|3.3|3.6 61.3|−3|0.4|3 33.7|2|−2|2.9 14.9|8.9|−2.3|9.2 148 10%of 7 20% of 36 55% of 44 86.2|−6|6|8.5 60.7|−3.9|8.9|9.7 29|2.4|7.1|7.514.5|6.5|2.4|6.9 149 10% of 7 35% of 40 40% of 44 82.7|−6.8|6.3|9.357.3|−2.4|9.6|9.9 28.2|2.3|7.4|7.7 14.9|2.1|0.9|2.3 150 15% of 7 10% of14 70% of 40 80.1|−7.4|6.5|9.9 55.8|0.4|8.7|8.7 28.3|4.7|3.4|5.815|0.5|−7|7 151 20% of 7 35% of 39 50% of 45 86.3|−5.3|4.3|6.965.1|−4|6.6|7.7 34.1|0.3|6.9|6.9 14.3|6.4|3|7.1 152 20% of 7 65% of 40 5% of 45 80.3|−7.5|6.2|9.7 55.7|−0.3|8.1|8.1 28|4.4|3.9|5.914.9|1.2|−4.2|4.4 153 25% of 7 40% of 9  75% of 13 80.4|−1.6|4.4|4.761.1|1.6|3.4|3.8 31.1|8.2|0.7|8.2 15|7.4|3.5|8.2 154 25% of 7 60% of 9 75% of 39 82.4|−2.7|2.4|3.6 61.6|−0.4|−0.3|0.6 33.7|2.4|−3.1|3.914.3|8.2|−2.8|8.6 155 30% of 7 15% of 31 45% of 39 83.3|−5|3.2|5.963.4|−4.7|−0.3|4.7 34.6|−4.6|0.4|4.6 13.8|6.2|−1.1|6.3 156 30% of 7 25%of 33 55% of 36 82.7|−5.9|4.5|7.4 60.9|−3.5|5.9|6.8 30.2|4.5|3.6|5.714.5|9.3|0|9.3 157 30% of 7 40% of 36 25% of 45 87.6|−6.8|5.7|8.964.3|−4.9|7.4|8.9 31.3|1.2|6.8|6.9 14|4.9|4.4|6.6 158 35% of 7 10% of 8 50% of 36 85.8|−6.9|5.2|8.6 62.7|−4.3|4.8|6.4 30.8|3.1|0.4|3.214.6|8.2|−5|9.6 159 35% of 7 15% of 9  55% of 36 86.9|−6.4|5.4|8.463|−3.7|4.7|5.9 30.1|3.6|1.4|3.9 13.8|7.3|−1|7.4 160 40% of 7 40% of 1210% of 31 86|−5.6|4.4|7.2 65.5|−5.9|3.8|7 34.9|−4.4|6.6|814.6|5.2|8.2|9.7 161 40% of 7 55% of 12 50% of 21 86.2|−5.2|3.5|6.365|−3.5|1.2|3.7 34.5|1.4|−2.8|3.1 14.9|8.9|−3.3|9.5 162 45% of 7 20% of8  45% of 12 83.5|−6.7|4.4|8 62.2|−6.4|4.6|7.9 32.7|−2.4|0.9|2.614.4|6.6|−2.7|7.1 163 25% of 8 20% of 26 35% of 40 80.9|−6.6|3.4|7.555.8|−0.7|3.9|4 26.8|5.9|−2.7|6.5 14.4|5.5|−7.3|9.2 164 30% of 8 30% of12 55% of 20 83.7|−0.6|3.8|3.9 64.2|−1.4|4.9|5.1 32.8|−1.7|−2.2|2.814.3|2.6|−7.8|8.3 165 30% of 8 55% of 14 45% of 43 81.2|−7|4.6|8.361.6|0.3|8.2|8.2 33.2|7|3.4|7.8 14.8|6.2|−7.3|9.5 166 50% of 8  5% of 1030% of 26 80|−7.3|2.7|7.8 56.3|−7.6|3.5|8.4 27.6|−6.7|−2.9|7.314.8|−6.4|−3.6|7.4 167 50% of 8  5% of 17 30% of 26 80.8|−8|2|8.257|−8.2|2.4|8.5 28|−7.1|−4.3|8.3 14.9|−6.2|−5.5|8.3 168 50% of 8 30% of26  5% of 35 80.1|−7.1|3.1|7.7 56.4|−7.2|3.8|8.1 27.6|−6.3|−2.3|6.714.7|−6.4|−3.1|7.1 169 50% of 8 30% of 26  5% of 37 80.5|−7.7|2.4|8.156.6|−7.1|2.8|7.6 27.4|−4.4|−4|5.9 14.4|−2.3|−5.4|5.9 170 50% of 8 30%of 26  5% of 38 80.8|−7.9|2.6|8.3 57|−7.8|3|8.3 27.9|−6.4|−3.8|7.514.9|−5.9|−5.2|7.9 171 50% of 8 30% of 26  5% of 39 80.9|−7.4|2.2|7.756.8|−6.6|2.2|6.9 27.7|−4|−4.9|6.3 14.7|−2|−6.6|6.9 172 50% of 8 30% of26  5% of 43 80.5|−7.6|2.1|7.9 55.9|−6|2.1|6.4 26.7|−2.1|−5.2|5.614|0.4|−6.7|6.7 173 55% of 8  5% of 14 30% of 26 80.6|−8.3|3.2|8.956.7|−8.5|5|9.9 27.6|−8|−0.7|8.1 14.6|−8.8|−1.7|8.9 174 15% of 9 30% of12 90% of 38 80.2|−5.8|6.1|8.4 65.6|−3.9|6.5|7.6 37.1|0.7|3.2|3.213.9|5.6|−3.4|6.6 175 15% of 9 80% of 13 40% of 16 80.2|−4.9|5.5|7.462.1|−4.5|5.3|6.9 31.9|−3.1|1.2|3.3 15|−7.3|−1.4|7.5 176 15% of 9  5% of24 95% of 41 80.3|2.2|−5.3|5.7 68.4|−2.9|−2.9|4.1 39.3|−9.3|−1.3|9.414.9|−8.6|−4.1|9.5For Examples 177 and 178, the molarity values were calculated based onan assumed 5 ml total solution volume. Volume changes due to componentsdissolved in the 5 ml of solvent were not considered.

Example 177

A solution was prepared which was 0.004M FeBr₂ and 6.39M water in γ-BL.The solution was placed in a cuvette and the absorption spectra weremeasured at various temperatures against a cuvette containing only γ-BL.The absorbance values at several values of λ_(max) and temperaturesvalues are given below: TABLE 10 λ_(max) 25 C. 45 C. 65 C. 85 C. 4700.71 1.25 2.72 5.00 606 0.09 0.10 0.13 0.12 712 0.03 0.03 0.06 0.06 7800.02 0.03 0.05 0.07

Example 178

A solution was prepared which was 0.004M FeBr₂, 6.4M water and 0.02Mdi(pentaerythritol) in γ-BL. The solution was placed in a cuvette andthe absorption spectra were measured at various temperatures against acuvette containing only γ-BL. The absorbance values at several values ofλ_(max) and temperatures values are given below: TABLE 11 λ_(max) 25 C.45 C. 65 C. 85 C. 402 0.88 1.37 2.87 5.00 471 0.29 0.80 2.32 5.00 6070.04 0.04 0.04 0.07

Examples 177 and 178 disclose systems which show an interesting case forthermochromic activity with Fe(II) going to what is believed to be theHεMLC form FeBr₄ ²⁻ on heating.

Exchange Metal Examples 179 to 188

In each case the solution was prepared by dissolving the materials in 5milliliters of the solvent listed. Some of the solution was placed in a1 cm borosilicate cuvette, a small stir bar was placed in the cuvetteand the cuvette was placed in the sample beam of a Shimadzu UV-3101 PCspectrophotometer. The solution was stirred and heated and thetemperature was monitored with a thermocouple immersed in the solutionin the cuvette. A similar, unheated 1 cm cuvette containing only thesolvent was placed in the reference beam of the spectrophotometer. Theabsorbance, A_(L), at a lower temperature, T_(L), and the absorbance,A_(H), at a higher temperature, T_(H), for various wavelengths ofmaximum absorbance, λ_(max), are given for Examples 179 to 188 involvingexchange metals in Table 12. For examples 179 to 188, the molarityvalues were calculated based on an assumed 5 ml total solution volume.Volume changes due to components dissolved in the 5 ml of solvent werenot considered.

Each solution was cycled back and forth between hot and cold severaltimes and the amount of TC activity remained consistent. On cooling thesolution decreased back to its original color and appearance and theabsorbance decreased back to its original level.

Example 179

A dark blue solution was prepared in γ-BL containing 0.01M Co(BF₄)₂:6H₂Oand 0.15M tri-n-butylphosphine oxide. Making the solution 0.039M inZn(CF₃SO₃)₂ caused it to change to light purple. On heating, thesolution turned progressively darker blue.

Example 180

A green solution was prepared in propylene carbonate containing 0.01MCo(BF₄)₂:6H₂O and 0.34M NaI. Making the solution 0.113M in Zn(CF₃SO₃)₂caused it to change to nearly colorless. On heating, the solution turnedprogressively darker green. A significant portion of the change inabsorbance of this system takes place in the near infrared.

Example 181

A purple solution was prepared in γ-BL containing 00.1M Co(BF₄)₂:6H₂Oand 0.032M 2,2′-ethane-1,2-diylbis(1-benzyl-1H-benzimidazole). Makingthe solution 0.016M in Zn(CF₃SO₃)₂ caused it to change to light purple.On heating, the solution turned progressively darker purple.

Example 182

A dark blue solution was prepared in γ-BL containing 0.01M Co(BF₄)₂:6H₂Oand 0.10M tetrabutylammonium thiocyanate. Making the solution 0.044M inZn(CF₃SO₃)₂ caused it to change to light purple. On heating, thesolution turned blue and became progressively darker blue.

Example 183

A dark blue solution was prepared in γ-BL containing 0.01M CoBr₂ and0.064M TBA[(4-MeOPh)₂PO₂]. Making the solution 0.036M in Zn(CF₃SO₃)₂caused it to change to light purple. On heating, the solution turnedblue and became progressively darker blue.

Example 184

A dark red solution was prepared in γ-BL containing 0.002M NiT₂ and0.12M NaI.

Making the solution 0.037M in Zn(CF₃SO₃)₂ caused it to change to lightyellow. On heating, the solution turned progressively darker orange-red.On cooling the solution changed back to its original light yellowappearance and the absorbance decreased back to its original level.

Example 185

A bright green solution was prepared in γ-BL containing 0.00125MCu(NO₃)₂:2.5H₂O, 0.006M Co(BF₄)₂:6H₂O and 0.095M TEACl:H₂O. Addition ofsome ZnCl₂ caused the solution to change to dark blue green. Furtheraddition of ZnCl₂ until the solution was 0.145M in ZnCl₂ caused thesolution to turn very light tan. On heating, the solution turnedprogressively darker blue green.

Example 186

A blue solution was prepared in γ-BL containing 0.022M Ni(NO₃)₂:6H₂O and0.18M TEACl:H₂O. Making the solution 0.1M in MnCl₂ caused it to changeto light green. On heating, the solution turned progressively darkergreen and the absorbance, in a 1 cm cuvette, increased at certainwavelengths and decreased at another wavelength as shown in Table 12.

Example 187

A blue solution was prepared in γ-BL containing 0.02M Ni(ClO₄)₂:6H₂O and0.20M TBABr. Making the solution 0.19M in MnBr₂ caused it to change toyellow. On heating, the solution turned green and became progressivelydarker green.

Example 188

A light red solution was prepared in γ-BL containing 0.01 MCu(NO₃)₂:2.5H₂O, 0.09 M TEACl:H₂O and 0.32 M ZnCl₂. On heating, thesolution turned progressively darker red. TABLE 12 EXM Exampleλ_(max)|A_(L)|T_(L)|A_(H)|T_(H) λ_(max)|A_(L)|T_(L)|A_(H)|T_(H)λ_(max)|A_(L)|T_(L)|A_(H)|T_(H) 179 548|0.17|25|0.66|85586|0.17|25|0.87|85 635|0.15|25|1.01|85 180 383|0.93|25|5.0|85745|0.28|25|3.07|85 181 528|0.32|25|0.63|85 561|0.41|25|0.89|85597|0.26|25|0.66|85 182 564|0.10|25|0.27|85 620|0.112|25|0.48|85640|0.102|25|0.48|85 183 533|0.19|25|0.49|85 589|0.20|25|0.73|85641|0.25|25|0.98|85 184 517|0.09|25|1.00|85 724|0.01|25|0.14|85 185475|0.22|25|0.87|85 585|0.093|25|0.61|85 680|0.166|25|1.10|85 186444|0.68|25|0.49|85 619|0.25|25|1.0|85 705|0.34|25|0.83|85 187470|1.57|25|1.51|85 649|0.34|25|1.75|85 719|0.28|25|0.99|85 188470|0.22|25|1.34|85 853|0.72|25|0.76|85

A variety of polymers may be used as part of LETC system. The use ofseveral of these polymers to make films that were then used to makelaminates is described in the following examples. The absorbances atseveral temperature for the laminated made from the systems of Examples189-214 are shown in Table 13.

Example 189

A LETC layer of cellulose acetate butyrate, (M_(w) c.a. 200,000;content: 17% butyryl, 29.5% acetyl, 1.5% hydroxyl), containing 0.1 molalCoCl₂, 2.6 molal LiCl and 3.2 molal ZnCl₂ was solvent cast from2-butanone onto a sheet of glass. After the solvent was removed, anothersheet of glass was pressed onto the layer to give a layer thickness of0.043 cm.

Example 190

A LETC layer of poly(vinyl alcohol-co-ethylene), (content: 27 mole %ethylene), containing 0.2 molal NiBr₂:xH₂O, 2.0 molal TBABr, 0.2 molal4-(3-PhPr)Pyr and 1.0 molal TMOLP was solvent cast from 50% water -50%n-propanol onto a sheet of glass. After the solvent was removed, anothersheet of glass was pressed onto the layer to give a layer thickness of0.078 cm.

Example 191

A LETC system in a urethane layer was prepared by mixing 28.9 wt %molten TMOLP 7.2 wt % g-BL 14.5 wt % diethyleneglycol and 49.4 wt %Bayer Desmodur® N-3200 to give a isocyanate to hydroxyl ratio of 0.3to 1. This polyurethane forming solvent system was made 0.12 molal inCoBr₂ and 0.47 molal in LiBr. The layer was allowed to cure betweensheets of glass to give a layer thickness of 0.078 cm.

Example 192

A LETC system in a urethane layer was prepared by mixing 31.2 wt %molten TMOLP 15.6 wt % diethyleneglycol and 53.2 wt % Bayer Desmodur®N-3200 to give a isocyanate to hydroxyl ratio of 0.3 to 1. Thispolyurethane forming solvent system was made 0.06 molal in CoBr₂ and0.50 molal in LiBr. The layer was allowed to cure between sheets ofglass to give a layer thickness of 0.075 cm.

Example 193

A LETC system in a urethane layer was prepared by mixing 42.8 wt %molten TMOLP and 57.2 wt % Bayer Desmodur® N-3200 to give a isocyanateto hydroxyl ratio of 0.33 to 1. This polyurethane forming solvent systemwas made 0.11 molal in CoBr₂, 0.46 molal in LiBr and 0.23 molalN-propyl-2,2′-dipyridylamine. The layer was allowed to cure betweensheets of glass to give a layer thickness of 0.090 cm.

Example 194

A LETC system in a urethane layer was prepared by mixing 32.1 wt %molten TMOLP, 16.0 wt % γ-BL and 51.9 wt % Bayer Desmodur® N-3200 togive a isocyanate to hydroxyl ratio of 0.4 to 1. This polyurethaneforming solvent system was made 0.13 molal in NiBr₂:xH₂O and 0.92 molalin TBABr. The layer was allowed to cure between sheets of glass to givea layer thickness of 0.075 cm.

Example 195

A LETC system in a urethane layer was prepared by mixing 33.9 wt %molten TMOLP, 11.3 wt % dimethylphthalate and 54.8 wt % Bayer Desmodur®N-3200 to give a isocyanate to hydroxyl ratio of 0.4 to 1. Thispolyurethane forming solvent system was made 0.10 molal in NiCl₂:6H₂O,0.65 molal in TBACl and 0.18 molal 4-tert-butylpyridine. The layer wasallowed to cure between sheets of glass to give a layer thickness of0.075 cm.

Example 196

A LETC system in a urethane layer was prepared by mixing 27.2 wt %molten TMOLP, 6.8 wt % dimethylphthalate and 66.0 wt % Bayer Desmodur®N-3200 to give a isocyanate to hydroxyl ratio of 0.6 to 1. Thispolyurethane forming solvent system was made 0.11 molal inNi(NO₃)₂:6H₂O, 1.10 molal in TBAI and 0.11 molal 4-tert-butylpyridine.The layer was allowed to cure between sheets of glass to give a layerthickness of 0.075 cm.

Example 197

A LETC system in a urethane layer was prepared by mixing 28.4 wt %molten TMOLP, 14.2 wt % γ-BL and 57.4 wt % Bayer Desmodur® N-3200 togive a isocyanate to hydroxyl ratio of 0.5 to 1. This polyurethaneforming solvent system was made 0.25 molal in NiBr₂:xH₂O, 0.82 molal inTBABr and 0.51 molal 2-(2-dimethylaminoethyl)pyridine. The layer wasallowed to cure between sheets of glass to give a layer thickness of0.075 cm.

Example 198

A LETC system in a urethane layer was prepared by mixing 27.2 wt %molten TMOLP, 6.8 wt % dimethylphthalate and 66.0 wt % Bayer Desmodur®N-3200 to give a isocyanate to hydroxyl ratio of 0.6 to 1. Thispolyurethane forming solvent system was made 0.11 molal inNi(NO₃)₂:6H₂O, 0.03 molal Co(NO₃)₂:6H₂O and 1.10 molal in TBAI. Thelayer was allowed to cure between sheets of glass to give a layerthickness of 0.063 cm.

Example 199

A LETC layer of hydroxypropylcellulose, (M_(w) c.a. 80,000), containing0.10 molal CoBr₂, 2.0 molal LiBr, 0.22 molal N—Pr-DPamine and 4.0 molalTMOLP was solvent cast from n-propanol onto a sheet of glass. After thesolvent was removed, another sheet of glass was pressed onto the layerto give a layer thickness of 0.048 cm.

Example 200

A LETC layer of hydroxypropylcellulose, (M_(w) c.a. 80,000), containing0.10 molal NiBr₂:xH₂O, 4.0 molal LiBr and 2.0 molal TMOLP was solventcast from n-propanol onto a sheet of glass. After the solvent wasremoved, another sheet of glass was pressed onto the layer to give alayer thickness of 0.053 cm.

Example 201

A LETC layer of hydroxypropylcellulose, (M_(w) c.a. 80,000), containing0.40 molal NiBr₂:xH₂O, 4.0 molal LiBr, 0.44 molal N—Pr-DPamine and 0.50molal TMOLP was solvent cast from n-propanol onto a sheet of glass.After the solvent was removed, another sheet of glass was pressed ontothe layer to give a layer thickness of 0.053 cm.

Example 202

A LETC layer of hydroxypropylcellulose, (M_(w) c.a. 80,000), containing0.40 molal NiBr₂:xH₂O, 2.0 molal TBABr, 1.2 molal 1-MeBIMZ and 1.75molal TMOLP was solvent cast from n-propanol onto a sheet of glass.After the solvent was removed, another sheet of glass was pressed ontothe layer to give a layer thickness of 0.058 cm.

Example 203

A LETC layer of hydroxypropylcellulose, (M_(w) c.a. 80,000), containing0.07 molal NiI₂:6H₂O, 1.0 molal LiT, 0.35 molal Ph₃P and 0.7 molal TMOLPwas solvent cast from n-propanol onto a sheet of glass. After thesolvent was removed, another sheet of glass was pressed onto the layerto give a layer thickness of 0.050 cm.

Example 204

A LETC layer of poly(methyl methacrylate), (M_(w) 996,000), containing0.10 molal Ni(NO₃)₂:6H₂O and 2.0 molal TBAI was solvent cast from2-butanone onto a sheet of glass. After the solvent was removed, anothersheet of glass was pressed onto the layer to give a layer thickness of0.030 cm.

Example 205

A LETC layer of linear poly(2-vinylpyridine), (M_(w) ca. 40,000),containing 0.60 molal Ni(NO₃)₂:6H₂O, 4.0 molal LiBr and 4.0 molal TMOLPwas solvent cast from ethanol onto a sheet of glass. After the solventwas removed, another sheet of glass was pressed onto the layer to give alayer thickness of 0.048 cm.

Example 206

A LETC layer of poly(vinyl acetate), (M_(w) ca. 167,000), containing0.40 molal Ni(NO₃)₂:6H₂O, 4.0 molal LiBr and 3.0 molal TMOLP was solventcast from ethanol onto a sheet of glass. After the solvent was removed,another sheet of glass was pressed onto the layer to give a layerthickness of 0.060 cm.

Example 207

A LETC layer of poly(vinyl alcohol), (M_(w) 13,000-23,000; 87-89%hydrolyzed), containing 0.40 molal Ni(NO₃)₂:6H₂O, 4.0 molal LiBr and 3.0molal TMOLP was solvent cast from water onto a sheet of glass. After thesolvent was removed, another sheet of glass was pressed onto the layerto give a layer thickness of 0.055 cm.

Example 208

A LETC layer of poly(vinyl alcohol), (M_(w) 13,000-23,000; 87-89%hydrolyzed), containing 0.20 molal CoBr₂ and 0.81 molal LiBr was solventcast from water onto a sheet of glass. After the solvent was removed,another sheet of glass was pressed onto the layer to give a layerthickness of 0.060 cm.

Example 209

A LETC layer of poly(vinyl alcohol), (M_(w) 13,000-23,000; 87-89%hydrolyzed), containing 0.20 molal CoBr₂, 0.81 molal LiBr and 1.0 molalNPG was solvent cast from water onto a sheet of glass. After the solventwas removed, another sheet of glass was pressed onto the layer to give alayer thickness of 0.078 cm.

Example 210

A LETC layer of poly(vinyl alcohol), (M_(w) 13,000-23,000; 87-89%hydrolyzed), containing 0.20 molal CoBr₂, 0.81 molal LiBr and 1.0 molal1,3-butanediol was solvent cast from water onto a sheet of glass. Afterthe solvent was removed, another sheet of glass was pressed onto thelayer to give a layer thickness of 0.078 cm.

Example 211

A LETC layer of poly(vinyl alcohol), (M_(w) 13,000-23,000; 87-89%hydrolyzed), containing 0.40 molal NiBr₂:xH₂O, 4.0 molal TBABr and 0.5molal 1,3-butanediol was solvent cast from water onto a sheet of glass.After the solvent was removed, another sheet of glass was pressed ontothe layer to give a layer thickness of 0.088 cm.

Example 212

A LETC layer of poly(vinyl alcohol), (M_(w) 13,000-23,000; 87-89%hydrolyzed), containing 0.40 molal NiCl₂:6H₂O and 4.0 molal cholinechloride was solvent cast from water onto a sheet of glass. After thesolvent was removed, another sheet of glass was pressed onto the layerto give a layer thickness of 0.088 cm.

Example 213

A LETC layer of poly(N-vinylpyrrolidone), (M_(w) ca. 55,000), containing0.20 molal CoBr₂, 2.0 molal LiBr, 2.0 molal N-propyl-2,2′-dipyridylamineand 4.0 molal TMOLP was solvent cast from ethanol onto a sheet of glass.After the solvent was removed, another sheet of glass was pressed ontothe layer to give a layer thickness of 0.053 cm.

Example 214

A LETC layer of poly(N-vinylpyrrolidone), (M_(w) ca. 55,000), containing0.40 molal Ni(NO₃)₂:6H₂O, 4.0 molal LiBr and 2.0 molal TMOLP was solventcast from ethanol onto a sheet of glass. After the solvent was removed,another sheet of glass was pressed onto the layer to give a layerthickness of 0.050 cm. TABLE 13 Absorbance Values as a Function ofTemperature at a λ_(max) in nm Ex. # λ_(max) 25 C. 45 C. 65 C. 85 C. 189671 0.06 0.11 0.20 0.40 190 633 0.16 0.38 0.73 1.23 191 700 0.70 1.572.38 3.17 192 700 0.38 1.22 2.04 2.73 193 638 0.04 0.20 0.55 1.12 194698 0.10 0.34 0.71 1.17 195 555 0.04 0.20 0.36 0.82 196 524 0.04 0.521.46 2.81 197 526 0.03 0.14 0.39 0.71 198 508 0.02 0.15 0.53 1.66 7821.60 1.90 1.96 2.10 199 642 0.08 0.31 0.64 1.01 200 700 0.17 0.39 0.831.36 201 498 0.11 0.47 0.77 1.03 202 600 0.15 0.49 1.02 1.49 203 5610.17 0.32 0.67 1.33 204 506 0.13 0.33 0.96 1.98 205 552 0.11 0.24 0.430.60 206 698 0.13 0.28 0.52 0.96 207 665 0.10 0.25 0.55 0.88 208 7020.65 0.66 1.00 1.87 209 701 0.30 0.41 0.87 1.73 210 701 0.31 0.44 1.191.90 211 705 0.11 0.37 0.73 1.20 212 653 0.26 0.64 1.35 2.08 213 6420.17 0.48 1.12 1.62 214 703 0.13 0.28 0.56 0.84

Examples of various LETC system prepared by solvent casting with varioustypes of PVB are given in Table 14. The Butvar® and Solutia® type PVB'sare available from Solutia Incorporated of Saint Louis, Mo. The CCPB-1776 is available from Chang Chun Petrochemical Co. Ltd. of Taipei,Taiwan. The Aldrich PVB is available from Aldrich Chemical Company ofMilwaukee, Wis. The numbers in front of the materials in the table aremolal concentration with the PVB being the main solvent in each case.Satisfactory to excellent LETC layers were obtained with these varioussamples. TABLE 14 Hydroxyl Ex. # Metal Salt HεL(1) HεL(2) LεL(1) PVBType Content 215  0.4 m NiBr₂ 2.02 m 1.75 m Butvar ® B-72 17.5-20.0%xH₂0 TBABr TMOLP wt 216  0.4 m NiBr₂ 2.02 m 1.75 m Butvar ® B-7417.5-20.0% xH₂0 TBABr TMOLP wt 217  0.4 m NiBr₂ 2.02 m 1.75 m Butvar ®B-76 11.0-13.0% xH₂0 TBABr TMOLP wt 218  0.4 m NiBr₂ 2.02 m 1.75 mButvar ® B-79 10.5-13.0% xH₂0 TBABr TMOLP wt 219  0.4 m NiBr₂ 2.02 m1.75 m Butvar ® B-90 18.0-20.0% xH₂0 TBABr TMOLP wt 220  0.4 m NiBr₂2.02 m 1.75 m Butvar ® B-98 18.0-20.0% xH₂0 TBABr TMOLP wt 221 0.07 m0.7 m TBAI 0.2 m 0.4 m TMOLP Solutia ® RA- N/A NiI₂(Ph₃P)₂ PPh3 41 2220.07 m 0.7 m TBAI 0.2 m 0.4 m TMOLP Solutia ® N/A NiI₂(Ph₃P)₂ PPh3 DMJ1223 0.07 m NiI₂ 0.75 m Butvar ® N/A xH₂0 TBAI SBTG 224 0.07 m NiI₂ 0.75m CCP B-1776 N/A xH₂0 TBAI 225 0.07 m NiI₂ 0.75 m Aldrich N/A xH₂0 TBAI18,2567

Examples 226 to 278 in Table 15 involve extrusion with various LETCsystems which comprise Butvar®B-90 as solid polymer solvent. Extrusionswere made with a Brabender conical twin screw extruder with counterrotating screws. In example 263 the powders were first extruded as ropeand the rope was chopped into pellets. The pellets were fed back intothe extruder and a very uniform film was produced for thickness or gageand for uniformity of composition and coloration, i.e. uniform opticaldensity when heated as part of a laminate between sheets of glass.Laminates were made, from each film placed between two pieces of plainglass, in a heated platen press or by heating in a heated vacuum bag.All of the laminates showed good thermochromic activity when heated byvarious means and good durability when exposed to sunlight, especiallythose containing stabilizer additives. When films were extruded fromformulations, where the metal ions were added as a complex, it waseasier to maintain constant feed of the powders into the extruder andthere was an improvement in the uniformity of the extruded film.Laminates that were prepared from films made from powders dried beforefeeding into the extruder, (see Notes in Table 15), showed improvedperformance and had better durability during sunlight exposure. TABLE 15Extruder Examples Metal Ex. # Salt/Complex HεL HεL LεL Additive(s)* Note226 0.20 m NiBr₂ 2.0 m 0.50 m xH₂0 TBABr TMOLP 227 0.07 m NiI₂ xH₂0 0.7m TBAI 0.35 m Ph₃P 0.40 m TMOLP 228 0.07 m NiI2 xH₂0 0.75 m TBAI 2290.20 m NiBr₂ 2.0 m 0.60 m 1- 1.25 m xH₂0 TBABr MeBIMZ TMOLP 230 0.07 mNiI₂ xH₂0 0.75 m TBAI 231 0.20 m CoBr₂ 0.81 m LiBr 2.09 m TMOLP 232 0.07m Co(NO₃)₂ 0.70 m 0.70 m Ph₃P 1.0 m TMOLP 6H₂O TBAI 233 0.20 m NiBr₂0.60 m 0.40 m 1- 0.50 m xH₂0 TBABr MeBIMZ TMOLP 234 0.10 m CoBr₂ 0.60 m1.75 m TBABr TMOLP 235 0.20 m NiBr₂ 0.60 m 0.40 m 1- 3.50 m NPG xH₂0TBABr MeBIMZ 236 0.20 m NiBr₂ 0.60 m 0.40 m 1- 3.0 m NPG dried xH₂0TBABr MeBIMZ 237 0.20 m NiBr₂ 0.60 m 0.40 m 1- 3.22 m NPG xH₂0 TBABrMeBIMZ 238 0.07 m NiBr₂ 0.7 m TBAI 0.35 m Ph₃P 0.40 m xH₂0 TMOLP 2390.20 m NiBr₂ 0.60 m 0.40 m 1- 1.93 m NPG xH₂0 TBABr EtBIMZ 240 0.10 mNiBr₂ 0.60 m 0.40 m 1- 2.5 m NPG xH₂0 TBABr EtBIMZ 241 0.10 m NiBr₂ 0.80m 0.80 m Ph₃P 0.80 m xH₂0 TBABr TMOLP 242 0.07 m 0.70 m 0.20 m Ph₃P 0.40m NiI₂(Ph₃P)₂ TBAI TMOLP 243 0.17 m Ni(1- 0.60 m 0.06 m 1- 1.93 m NPGEtBIMZ)₂Br₂ TBABr EtBIMZ 244 0.07 m 0.70 m 0.20 m Ph₃P 2.5 m NPGNiI₂(Ph₃P)₂ TBAI 245 0.10 m CoBr₂ 0.60 m 2.25 m 0.50% Tinuvin TBABrTMOLP 326 246 0.20 m NiBr₂ 2.0 m 1.00 m xH₂0 TBABr TMOLP 247 0.17 mNi(1- 1.00 m LiBr 1.75 m NPG EtBIMZ)₂Br₂ 248 0.17 m Ni(1- 100 m LiBr0.50 m EtBIMZ)₂Br₂ TMOLP 249 0.20 m 1.00 m 0.40 m 1- 0.50 m NiI₂(Ph₃P)₂TBAI EtBIMZ TMOLP 0.20 m PPh3 250 0.10 m CoBr₂ 0.60 m 2.25 m TBABr TMOLP251 0.07 m 0.70 m 0.20 m Ph₃P 0.40 m NiI₂(Ph₃P)₂ TBAI TMOLP 252 0.17 mNi(1- 0.60 m 1.93 m NPG EtBIMZ)₂Br₂ TBABr 253 0.20 m Ni(1- 0.60 m 0.50 mEtBIMZ)₂Br₂ TBABr TMOLP 254 0.07 m 0.70 m 0.20 m Ph₃P 0.40 m 0.14%Tinuvin NiI₂(Ph₃P)₂ TBAI TMOLP 144 255 0.20 m Ni(1- 0.60 m 1.93 m NPG0.47% Tinuvin EtBIMZ)₂Br₂ TBABr 405 256 0.10 m CoBr₂ 0.60 m 2.25 m 0.52%Tinuvin TBABr TMOLP 405 257 0.07 m 0.70 m 0.20 m Ph₃P 0.40 m 0.49%Tinuvin dried NiI₂(Ph₃P)₂ TBAI TMOLP 144 258 0.20 m NiBr₂ 2.0 m 0.50 m0.50% Tinuvin xH₂0 TBABr TMOLP 405 259 0.20 m NiBr₂ 2.0 m 4.00 m NPG0.41% Tinuvin xH₂0 TBABr 405 260 0.07 m 0.70 m 0.20 m Ph₃P 0.40 m 0.49%Tinuvin dried NiI₂(Ph₃P)₂ TBAI TMOLP 144 261 0.20 m Ni(1- 0.60 m 1.93 mNPG 0.47% Tinuvin EtBIMZ)₂Br₂ TBABr 405 262 0.20 m Ni(1- 0.60 m 1.93 mNPG 0.42% Tinuvin EtBIMZ)₂Br₂ TBABr 405 10% Plasticizer** 263 0.20 mNi(1- 0.60 m 1.93 m NPG 0.47% Tinuvin from EtBIMZ)₂Br₂ TBABr 405 pellets264 0.07 m 0.70 m 0.20 m Ph₃P 0.60 m 0.48% Tinuvin dried NiI₂(Ph₃P)₂TBAI TMOLP 144 265 0.20 m Ni(1- 0.60 m 1.93 m NPG 0.47% Tinuvin driedEtBIMZ)₂Br₂ TBABr 405 266 0.20 m NiBr₂ 2.0 m 1.25 m 0.50% Tinuvin driedxH₂0 TBABr TMOLP 326 267 0.20 m Ni(1- 0.60 m 1.93 m NPG 0.47% Tinuvindried EtBIMZ)₂Br₂ TBABr 405 268 0.20 m NiBr₂ 2.0 m 1.25 m 0.50% Tinuvindried xH₂0 TBABr TMOLP 326 269 0.07 m 0.70 m 0.20 m Ph₃P 0.60 m 0.48%Tinuvin dried NiI₂(Ph₃P)₂ TBAI TMOLP 144 270 0.07 m 0.70 m 0.20 m Ph₃P0.60 m 0.50% Tinuvin dried NiI₂(Ph₃P)₂ TBAI TMOLP 144 271 0.20 m Ni(1-0.60 m 1.93 m NPG 0.50% Tinuvin EtBIMZ)₂Br₂ TBABr 326 272 0.20 m Ni(1-0.60 m 1.93 m NPG 0.50% Tinuvin dried EtBIMZ)₂Br₂ TBABr 144 273 0.20 mNiBr₂ 2.0 m 1.25 m 0.50% Tinuvin dried xH₂0 TBABr TMOLP 144 274 0.50%Tinuvin 326 275 0.07 m 0.70 m 0.20 m Ph₃P 0.50 m 0.50% Tinuvin driedNiI₂(Ph₃P)₂ TBAI TMOLP 144 276 0.07 m 0.70 m 0.20 m Ph₃P 0.50 m 0.50%Tinuvin dried NiI₂(Ph₃P)₂ TBAI TMOLP 144 277 0.50% Tinuvin 326 278 0.20m Ni(1- 0.60 m 1.93 m NPG 0.50% Tinuvin dried EtBIMZ)₂Br₂ TBABr 144*% given as weight % of total formulation**plasticizer = triethyleneglycol-bis(2-ethylhexonate)

FIGS. 51 to 57 relate to Examples 279 to 285. The figures show thespectra measured at 25 C, 45 C, 65 C and 85 C with an Ocean Optics 2000diode array spectrometer. For each spectrum in FIGS. 51 to 58, theabsorbance spectrum of a reference sample, made with the same type offloat glass and a plain piece of PVB film, was subtracted out. Thus thespectral data are for the LETC films alone. In each case the spectrumwith the lowest absorbance corresponds to 25 C, the next highestabsorbance spectrum corresponds to 45 C and so on such that the spectrumwith highest absorbance peaks in each figure corresponds to thatmeasured at 85 C. In all the FIGS. 51 to 58, the x axis, (horizontalaxis), gives the wavelengths in nanometers and the y axis, (verticalaxis), gives the absorbance values.

Example 279

A physically blended mixture of powders was made by stirring 38 grams ofNi(PPh₃)₂I₂, 165 grams of TBAI, 4.4 grams of Tinuvin® 144, 33 grams ofPPh₃ and 34 grams of TMOLP into 633 grams of PVB, (Butvar® B-90). Thismixture was extruded to give a LETC film which varied from about 0.03microns to about 0.09 centimeters thick. A piece of this film that was0.031 centimeters thick was used to laminate two sheets of plain floatglass together. The laminate was very light tan in color and changed todark red on heating. The spectrum of the laminate was measured at 25 C,45 C, 65 C and 85 C. By subtracting out a reference sample, the spectraldata for the film alone were calculated and plotted in FIG. 51.

Example 280

A physically blended mixture of powders was made by stirring 71.5 gramsof Ni(1-EtBIMZ)₂Br₂, 139.5 grams of TBABr, 5.0 grams of Tinuvin® 405 and144 grams of NPG into 715 grams of PVB, (Butvar® B-90). This mixture wasextruded to give a LETC film which varied from about 0.04 to about 0.09centimeters thick. A piece of this film that was 0.060 centimeters thickwas used to laminate two sheets of plain float glass together. Thelaminate was light blue in color and changed to dark blue on heating.The spectrum of the laminate was measured at 25 C, 45 C, 65 C and 85 C.By subtracting out a reference sample, the spectral data for the filmalone were calculated and plotted in FIG. 52.

Example 281

A physically blended mixture of powders was made by stirring 6.99 gramsof CoBr₂, 60.1 grams of TBABr and 73.6 grams of TMOLP into 313.0 gramsof PVB powder, (Butvar® B-90). This mixture was extruded to give a LETCfilm which varied from about 0.04 to about 0.09 centimeters thick. Apiece of this film that was 0.054 centimeters thick was used to laminatetwo sheets of plain float glass together. The laminate was nearlycolorless and changed to light blue on heating. The spectrum of thelaminate was measured at 25 C, 45 C, 65 C and 85 C. By subtracting out areference sample, the spectral data for the film alone were calculatedand plotted in FIG. 53.

Example 282

A physically blended mixture of powders was made by stirring 33.0 gramsof NiBr₂.xH₂O, 388.1 grams of TBABr, 5.7 grams of Tinuvin® 326, 5.7grams of Tinuvin® 144 and 100.9 grams of TMOLP into 600.7 grams of PVBpowder, (Butvar® B-90). This mixture was extruded to give film whichvaried from about 0.04 to about 0.11 centimeters thick. A piece of thisfilm that was 0.098 centimeters thick was used to laminate two sheets ofplain float glass together. The laminate was light green and changed tolight blue on heating. The spectrum of the laminate was measured at 25C, 45 C, 65 C and 85 C. By subtracting out a reference sample, thespectral data for the film alone were calculated and plotted in FIG. 54.

Example 283

A multilayer laminate was made with a 350 micron thick layer similar tothe material of example 279 and a 460 micron thick layer similar to thematerial of example 280. Prior to lamination, a 100 micron film ofpoly(ester terephthalate) was placed between the PVB films and the 3layers of film stack was laminated between 2 sheets of plain floatglass. The spectrum of the laminate was measured at 25 C, 45 C, 65 C and85 C. By subtracting out a reference sample, the spectral data for thefilm stack alone were calculated and plotted in FIG. 55. The values ofL*, a*, b* and Y for films making up the laminate are given in the Table16 at various temperatures. TABLE 16 Temperature (C.) 25 C. 45 C. 65 C.85 C. Y 91.5 79.7 45.6 12.4 a* −4.1 −4.0 −2.5 1.9 b* 4.0 5.6 8.4 12.3 c*5.7 6.8 8.8 12.5

Example 284

A multilayer laminate was made with a 350 micron thick layer similar tothe material of example 279, a 520 micron thick layer similar to thematerial of example 280 and a 220 micron thick layer similar to thematerial of example 281. Prior to lamination, 200 micron thick films ofpoly(ester terephthalate) were place between the films of PVB and the 5layers of film stack was laminated between 2 sheets of plain floatglass. The spectrum of the laminate was measured at 25 C, 45 C, 65 C and85 C. By subtracting out a reference sample, the spectral data for thefilm stack alone were calculated and plotted in FIG. 56. The values ofL*, a*, b* and Y for films making up the laminate are given in the Table17 at various temperatures. TABLE 17 Temperature (C.) 25 C. 45 C. 65 C.85 C. Y 82.8 66.0 29.0 5.3 a* −5.0 −6.6 −7.9 −6.7 b* 5.2 6.0 6.1 7.2 c*7.2 8.9 10.0 9.8

Example 285

A multilayer laminate was made with a 430 micron thick layer similar tothe material of example 279, a 300 micron thick layer similar to thematerial of example 280 and a 590 micron thick layer of the materialfrom example 282. Prior to lamination, 200 micron thick films ofpolycarbonate were place between the films of PVB and the 5 layers offilm stack was laminated between 2 sheets of plain float glass. Thespectrum of the laminate was measured at 25 C, 45 C, 65 C and 85 C. Bysubtracting out a reference sample, the spectral data for the film stackalone were calculated and plotted in FIG. 57. The values of L*, a*, b*and Y for films making up the laminate are given in the Table 18 atvarious temperatures. TABLE 18 Temperature (C.) 25 C. 45 C. 65 C. 85 C.Y 85.9 58.1 25.4 5.8 a* −8.0 −8.5 −8.6 −5.2 b* 6.3 6.9 5.7 8.7 c* 10.211.0 10.3 10.1

Example 286

Three laminates were prepared by laminating a film stack like thatdisclosed in Example 285, except that poly(ester-terephthalate) film wasused for the separators. These laminates were used as the center panesof a triple pane insulated glass units. The insulated glass units wereeach placed on a box to simulate a vertically glazed, window unit in abuilding. In each window unit, the pane that was closest to the interiorof the box had a Solarban® 60, low-e coating on the surface that facedthe center pane, thermochromic laminate. Solarban® 60 is available fromPPG of Pittsburgh, Pa. The exterior pane in each case was clear, i.e.plain glass. The air space between the exterior pane and thethermochromic laminate was 0.38 inches and the air space between thethermochromic laminate and low-e coated pane was 0.5 inches.

The window units were placed outdoors and exposed to sunlight. One ofthe window units was oriented to face east, one faced south and thethird faced west. During the day the directness of sunlight on eachwindow varied with the time of day as the earth rotated. The east facingwindow was observed to tint to a dark gray appearance in the morning,the south facing window tinted dark gray in during midday and westfacing window darkened to very dark gray in the late afternoon andevening. The experiment was conducted on a sunny day in Michigan inAugust. The visible, white light transmission value, Y, of each laminatehad previously been measured as a function of the temperature of thatlaminate. The temperature of each laminate was measured and recordedthroughout the day. The temperature measurements were used to calculatethe visible, white light transmission changes throughout the day due tosunlight exposure.

The calculated transmission data are plotted as a function the time ofday for each of the thermochromic laminates in FIG. 50. The curves inFIG. 50 show the remarkable sunlight responsiveness of our LETC systemsin our SRT™ configurations. This kind of response allows the windows todarken and provide energy savings any time of the day, any day of theyear and at any location or orientation on a building or vehicle. Thisresponse is just due to the directness of the sunlight and the windowtint just to the level desired to relieve heat load and glare, whilestill provide significant daylighting. Similar sunlight inducedthermochromic tinting has been observed on numerous occasions for triplepane units and even double pane units glazed into a building. Occupantsof the building experienced relief from heat load and glare duringdirect sunlight exposure of the windows.

In Examples 287 to 293, LETC layers were prepared by extrusion with thefollowing composition:

-   -   0.07 m NiI₂(Ph₃P)₂    -   0.7 m TBAI    -   0.2 m Ph₃P    -   0.4 m TMOLP    -   0.49 wt % Tinuvin® 144    -   in Butvar® B-90 PVB

The layers were treated as described below and the durability of thelaminates was tested for long term exposure at 80 C. Tables 19 to 25give the measured absorbance values at 25 C and 85 C at 425 nm and 565nm as a function of time for the laminate of the LETC layer in an 80 Coven in the dark.

Example 287

The LETC layer was exposed to room humidity for 24 hours and then waslaminated between two pieces of glass and the edge was sealed withepoxy. The absorbance data in Table 19 show a significant increase inthe absorbances at both wavelengths and both measured temperatures as aresult of heat exposure. TABLE 19 Absorbance Hours Absorbance AbsorbanceAbsorbance 565 at 80 C. 425 nm|25 C. 425 nm|85 C. 565 nm|25 C. nm|85 C.0 0.10 1.17 0.06 0.57 409 0.19 2.06 0.08 1.03 1035 0.38 2.68 0.14 1.362591 0.80 2.70 0.25 1.38

Example 288

A piece of the LETC layer was laminated between pieces of glass shortlyafter the layer was extruded but without pre-drying the layer. Thelaminate was not sealed. The measured absorbances irreversibly increasedwith time at 80 C in the center of the laminate, as shown by the data inTable 20. Also, the unsealed edges of the layer turned colorless andthen yellow and showing no thermochromic activity. TABLE 20 AbsorbanceHours Absorbance Absorbance Absorbance 565 at 80 C. 425 nm|25 C. 425nm|85 C. 565 nm|25 C. nm|85 C. 0 0.17 2.85 0.09 1.40 362 0.42 3.10 0.162.06 1130 0.82 max 0.29 2.52 2998 1.32 max 0.42 2.60max ≈ 3.5 absorbance units

Example 289

Apiece of the LETC layer was vacuum dried at room temperature for about20 hours before lamination. The edge of the laminate was sealed withepoxy. This amount of drying had little impact on stability as seen bythe irreversible absorbance increases over time in the Table 21. TABLE21 Absorbance Hours Absorbance Absorbance Absorbance 565 at 80 C. 425nm|25 C. 425 nm|85 C. 565 nm|25 C. nm|85 C. 0 0.18 1.60 0.07 0.73 4090.39 2.65 0.12 1.59 1035 0.81 2.66 0.27 1.92 2591 1.72 2.82 0.57 1.90

Example 290

A piece of the LETC layer was extruded where all of the components werepre-dried prior to extrusion. The layer produced by extrusion was storedin vacuum over desiccant. This pre and post dried layer was laminatedbetween pieces of glass and the edges were sealed with epoxy. Themeasured absorbance values given in Table 22 show much greater stabilityfor thermochromic activity on exposure to 80 C. TABLE 22 AbsorbanceHours Absorbance Absorbance Absorbance 565 at 80 C. 425 nm|25 C. 425nm|85 C. 565 nm|25 C. nm|85 C. 0 0.23 1.82 0.10 0.87 640 0.23 1.85 0.090.85 1701 0.33 1.71 0.09 0.77 2393 0.39 1.69 0.09 0.72

Example 291

The experiment in Example 290 was repeated in another extrusion run theresulting laminate also showed improved stability as shown in the Table23. TABLE 23 Hours Absorbance Absorbance Absorbance Absorbance at 80 C.425|25 C. 425|85 C. 565|25 C. 565|85 C. 0 0.14 1.38 0.07 0.67 502 0.161.36 0.07 0.63 766 0.18 1.36 0.07 0.64 1847 0.19 1.45 0.07 0.65

Example 292

A thermochromic layer was prepared by solvent casting a thermochromiclayer from n-propanol. The layer contained:

-   -   0.07 m NiI₂(Ph₃P)₂    -   0.7 m TBAI    -   0.2 m Ph₃P    -   0.4 m TMOLP    -   0.49 wt % Tinuvin® 144    -   in Butvar® B-90 PVB

the molal value were only with respect to the amount of PVB, but theentire LETC layer was made 15 weight % in triethyleneglycolbis(2-ethylhexanoate). As part of the solvent casting process the layerwas thoroughly dried at 80 C under nitrogen. The layer was laminatedbetween pieces of glass and edge sealed with epoxy. The laminate showedimproved stability during storage at 80 C as shown by the absorbancevalues in Table 24. TABLE 24 Absorbance Hours Absorbance AbsorbanceAbsorbance 565 at 80 C. 425 nm|25 C. 425 nm|85 C. 565 nm|25 C. nm|85 C.0 0.17 1.99 0.11 0.94 2247 0.30 2.09 0.13 0.99 2967 0.33 2.10 0.14 1.023687 0.35 1.81 0.14 0.86

Example 293

A thermochromic layer like that in Example 292 was prepared except thetriethyleneglycol bis(2-ethylhexanoate) content of the layer was 20weight %. The laminate again showed improved stability during storage at80 C as shown by the absorbance values in Table 25. TABLE 25 AbsorbanceHours Absorbance Absorbance Absorbance 565 at 80 C. 425 nm|25 C. 425nm|85 C. 565 nm|25 C. nm|85 C. 0 0.22 2.40 0.14 1.18 2247 0.27 2.34 0.151.09 2967 0.27 2.15 0.15 1.07 3687 0.28 1.91 0.15 0.90

Example 294

Thermochromic layers with the following compositions: Composition AComposition B 0.1 m (TBA)₂NiI₄ 0.2 m (TBA)₂NiBr₄ 0.11 m 4-(3-PhPr)Pyr0.4 m 1-butylimidazole 0.3 m TBAI 0.2 m TBABr 0.005 m Ph₃P 0.5 m NPG0.07 m TMOLP in Butvar ® B-90 1 wt % Tinuvin ® 405 in Butvar ® B-90

were prepared by extrusion. A 0.03 cm thick layer with Composition A wasplaced on one side of a separator that was 0.0076 cm thick layer ofpoly(ester terephthalate) which was excited on both sides byglow-discharge and labeled as Southwall “HB3/75 Glow 2-sided” availablefrom Southwall Technologies Inc. of Palo Alto, Calif. Two layers withComposition B, totaling 0.09 cm thick, were placed on the other side ofthe separator. The polymer layer stack was placed between sheets ofclear, plain, soda-lime float glass and a laminate was formed in aheated vacuum bag. The spectrum of the laminate was measured at 25 C, 45C, 65 C and 85 C. By subtracting out a reference sample, the spectraldata for the film stack alone were calculated and plotted in FIG. 58.The values of L*, a*, b* and Y for films making up the laminate aregiven in the Table 26 at various temperatures. TABLE 26 Temperature (C.)25 C. 45 C. 65 C. 85 C. Y 75.6 61.1 29.8 7.9 a* −12.7 −13.9 −11.8 −5.1b* 16.2 12.4 5.7 4.4 c* 20.5 18.3 13.1 6.7

The information in Table 27 along with the key section of Table 27 givethe formulations of liquid solution LETC systems for Examples 295-1025.In each case the solution was prepared by dissolving the materialsindicated in 5 milliliters of the solvent listed at the heading of eachsection of Table 27. In each example, some of the solution was placed ina 1 cm borosilicate cuvette, a small stir bar was placed in the cuvetteand the cuvette was placed in the sample beam of a Shimadzu UV-3101PCspectrophotometer. The solution was stirred and heated and thetemperature was monitored with a thermocouple immersed in the solutionin the cuvette. A similar, unheated 1 cm cuvette containing only thesolvent was placed in the reference beam of the spectrophotometer. Theabsorption spectrum was measured at various temperatures and thewavelengths of maximum absorbance, λ_(max), and the absorbance at thesevalues of λ_(max) were recorded for each temperature of interest. Table27 shows the LETC performance at various temperatures for selectedvalues of λ_(max) in a format λ_(max)|A_(L)|T_(L)|A_(H)|T_(H). A_(L) isthe absorbance measured at a lower temperature, T_(L), and A_(H) is theabsorbance measured at a higher temperature, T_(H), at the λ_(max)indicated. For the examples in Table 27, the molarity values werecalculated based on an assumed 5 ml total solution volume. Volumechanges due to components dissolved in the 5 ml of solvent were notconsidered.

In Table 27 the Solvent May Act as Part or all of the LεL.

Each solution was cycled back and forth between hot and cold and theamount of TC activity appeared remained consistent, i.e. on cooling thesolution decreased back to its original color and appearance.

The key section also gives the synthesis for all the materials used inLETC systems that are not commercially available. TABLE 27 Ex.# [M] M[LeL] LeL [HeL] HeL Lmax|Al|Tl|Ah|Th Lmax|Al|Tl|Ah|Th Lmax|Al|Tl|Ah|ThSolvent = 1,3-Butanediol 295 0.025 Mi 0.09 Hga 596|0.156|25|1.843|85677|0.172|25|2.988|85 Solvent = 3-Hydroxypropionitrile 296 0.01 Mo 0.034Hik 591|0.152|25|1.1|85 628|0.13|25|1.033|85 680|0.17|25|1.396|85Solvent = Diethylene glycol 297 0.01 Mo 0.2 Hfx 532|0.37|25|0.595|85570|0.362|25|0.704|85 298 0.012 Mh 0.16 Hfz 618|0.21|25|1.051|85675|0.224|25|1.344|85 700|0.244|25|1.473|85 299 0.01 Mo 0.11 Hfy535|0.297|25|0.526|85 571|0.252|25|0.581|85 Solvent = e-Caprolactone 3000.01 Mo 0.92 Lbg 0.1 Hiu 537|0.309|25|0.635|85 301 0.01 Mh 0.03 Lu 0.27Hfz 665|0.054|25|1.05|85 701|0.046|25|1.582|85 724|0.045|25|1.745|85 3020.01 Mo 2.6 Lbg 0.15 Hgh 533|0.333|25|0.933|85 573|0.285|25|1.254|85 3030.01 Mo 1 Lbg 0.1 Hjx 546|0.19|25|0.446|85 585|0.127|25|0.539|85632|0.083|25|0.486|85 304 0.01 Mo 0.19 Lbg 0.1 Hgi 532|0.226|25|0.722|85570|0.158|25|0.981|85 Solvent = Ethylene Glycol 305 0.01 Mo 2 Hfx532|0.339|25|0.67|85 570|0.307|25|0.826|85 306 0.01 Mo 1 Hfx530|0.232|25|0.412|85 570|0.185|25|0.468|85 307 0.01 Mi 0.02 Hdy570|0.371|25|0.969|85 648|0.47|25|1.592|85 0.022 Hga 308 0.01 Mh 0.03Hdy 594|0.21|25|0.763|85 650|0.247|25|1.169|85 0.079 Hfz 309 0.01 Mh0.02 Hdy 630|0.188|25|0.966|85 665|0.24|25|1.314|85700|0.156|25|0.837|85 0.37 Hhv 310 0.01 Mi 0.03 Hdy 570|0.256|25|0.68|85648|0.245|25|0.937|85 Solvent = Gamma Butyrolactone 311 0.02 Mak 0.18Lbw 0.2 Hfz 705|1.467|25|3.47|85 756|1.467|25|3.372|85 312 0.02 Mak 0.32Lao 0.2 Hfz 672|0.111|25|2.099|85 704|0.133|25|2.583|85756|0.107|25|2.444|85 313 0.02 Mak 0.21 Lcg 0.2 Hfz 352|1.061|25|5|85704|0.175|25|2.012|85 756|0.154|25|1.958|85 314 0.02 Mak 0.35 Le 0.2 Hfz705|0.706|25|3.621|85 755|0.703|25|3.539|85 315 0.02 Mal 0.78 Lbs 0.06Hje 617|0.045|25|1.136|85 653|0.075|25|1.026|85 703|0.1|25|1.062|85 3160.01 Mo 2.2 Lck 0.04 Hgz 565|0.122|25|1.046|85 639|0.163|25|2.038|850.05 Hje 317 0.01 Mo 2.24 Lck 0.1 Hei 596|0.085|25|0.843|85633|0.072|25|0.804|85 675|0.074|25|0.99|85 0.02 Hje 318 0.02 Mal 0.28Lck 0.003 Hbt 541|0.085|25|0.496|85 665|0.118|25|0.591|85757|0.051|25|0.467|85 0.2 Hfz 0.003 Hbb 319 0.02 Mal 0.12 Lck 0.31 Hbj651|0.086|25|1.49|85 702|0.086|25|1.342|85 749|0.059|25|1.031|85 0.1 Hij320 0.02 Mal 0.33 Lck 0.01 Hbu 521|0.039|25|0.474|85630|0.257|25|1.738|85 987|0.073|25|0.263|85 0.02 Hdp 0.2 Hfz 321 0.02Mak 1.3 Lbg 0.16 Hfz 640|0.175|25|1.777|85 680|0.188|25|1.676|851026|0.104|25|0.801|85 0.044 Hke 322 0.02 Mal 0.15 Lck 0.01 Hbu520|0.067|25|0.999|85 702|0.252|25|1.556|85 758|0.212|25|1.553|85 0.2Hfz 323 0.02 Mal 0.23 Lck 0.02 Hra 521|0.34|25|2.698|85651|0.181|25|0.652|85 998|0.161|25|0.994|85 0.2 Hij 324 0.01 Mo 2.9 Lck0.02 Hgz 567|0.059|25|0.647|85 643|0.061|25|1.361|85 0.07 Hje 325 0.02Mal 0.15 Lck 0.02 Hde 483|0.053|25|0.295|85 703|0.112|25|0.92|85755|0.078|25|0.888|85 0.2 Hfz 326 0.02 Mak 0.43 Le 0.2 Hfz705|0.377|25|3.119|85 756|0.366|25|3.053|85 327 0.02 Mak 0.86 Lbg 0.1Hcb 577|0.151|25|0.839|85 617|0.205|25|0.962|85 657|0.232|25|0.849|850.04 Hje 328 0.02 Mal 0.23 Lck 0.2 Hcs 664|0.123|25|1.556|85705|0.131|25|1.763|85 753|0.108|25|1.649|85 0.2 Hfz 329 0.02 Mal 0.21Lck 0.3 Har 573|0.119|25|2.144|85 624|0.262|25|1.744|85990|0.069|25|0.604|85 0.06 Hij 330 0.02 Mal 0.41 Lck 0.02 Hcr588|0.115|25|0.662|85 646|0.137|25|0.59|85 0.06 Hij 331 0.01 Mo 2.4 Lbg0.15 Hgh 535|0.364|25|1.071|85 573|0.324|25|1.443|85 0.1 Hir 332 0.04Mak 1.7 Lbg 0.02 Hea 505|0.097|25|1.193|85 635|0.361|25|1.563|85985|0.182|25|0.85|85 0.32 Hfz 0.12 Hhh 333 0.01 Mo 3.3 Lbf 0.1 Hfl535|0.266|25|1.164|85 580|0.264|25|1.679|85 334 0.01 Mo 3 Lck 0.02 Hdp598|0.338|25|1.895|85 634|0.385|25|2.272|85 662|0.329|25|2.231|85 0.05Hje 335 0.02 Mal 0.27 Lck 0.05 Hcp 682|0.105|25|1.783|85725|0.095|25|1.902|85 0.1 Hij 336 0.003 Mal 0.1 Lck 0.003 Hij378|0.107|25|2.011|85 503|0.03|25|0.841|85 703|0.012|25|0.225|85 0.03Hir 0.03 Hke 337 0.005 Mo 0.28 Lck 0.05 Hir 618|0.064|25|0.609|85716|0.086|25|1.703|85 751|0.047|25|1.251|85 0.1 Hkf 338 0.02 Mak 0.49 Lk0.2 Hfz 705|0.427|25|3.312|85 757|0.41|25|3.132|85 339 0.02 Mak 0.49 Lbg0.043 Hfw 657|0.172|25|1.025|85 691|0.206|25|0.966|85 0.057 Hfz 340 0.02Mal 0.46 Lck 0.02 Hbv 555|0.083|25|0.64|85 636|0.139|25|0.83|85973|0.066|25|0.286|85 0.2 Hfz 341 0.01 Mo 2.4 Lck 0.1 Hgz565|0.101|25|1.039|85 635|0.113|25|1.893|85 0.05 Hje 342 0.02 Mak 0.78Lbg 0.044 Hn 625|0.243|25|1.782|85 650|0.257|25|1.739|85698|0.228|25|1.357|85 0.1 Hje 343 0.02 Mak 0.62 Lh 0.2 Hfz669|0.136|25|2.047|85 705|0.175|25|2.464|85 758|0.15|25|2.283|85 3440.01 Mo 2.6 Lbg 0.15 Hgh 593|0.258|25|1.46|85 0.02 Hje 345 0.02 Mak 0.53Lcm 0.2 Hfz 668|0.603|25|1.81|85 704|0.855|25|2.216|85756|0.844|25|2.096|85 346 0.01 Mal 0.13 Lck 0.02 Hdm 400|0.267|25|5|85518|0.043|25|3.299|85 700|0.064|25|0.794|85 0.1 Hir 0.02 Hke 347 0.02Mal 0.51 Lbs 0.04 Hje 580|0.03|25|0.597|85 616|0.049|25|0.708|85703|0.105|25|0.56|85 348 0.02 Mal 1.05 Lck 0.04 Hr 583|0.091|25|0.807|85630|0.134|25|0.663|85 990|0.061|25|0.24|85 0.2 Hij 349 0.02 Mal 0.25 Lck0.04 Hdo 636|0.137|25|1.21|85 0.1 Hfz 350 0.02 Mal 1.29 Lck 0.02 Hgr514|0.459|25|3.008|85 885|0.111|25|0.638|85 1000|0.215|25|1.151|85 0.2Hfz 351 0.01 Mo 1.49 Lck 0.05 Hgh 594|0.103|25|1.006|85630|0.146|25|1.64|85 694|0.159|25|1.932|85 0.1 Hje 352 0.02 Mal 0.041Lck 0.02 Hra 550|0.196|25|1.38|85 612|0.182|25|0.87|851017|0.096|25|0.406|85 0.02 Hir 353 0.01 Mo 1.7 Lck 0.1 Heh557|0.349|25|0.615|85 588|0.283|25|0.53|85 354 0.02 Mal 0.16 Lck 0.04Hbt 563|0.091|25|2.186|85 665|0.114|25|1.69|85 930|0.04|25|0.635|85 0.02Hfe 0.2 Hir 355 0.002 Mal 0.006 Lck 0.02 Hir 515|0.044|25|1.116|85724|0.009|25|0.166|85 356 0.02 Mal 0.13 Lck 0.02 Hdi356|0.226|25|2.272|85 645|0.083|25|0.305|85 0.04 Hij 357 0.02 Mal 0.21Lck 0.2 Hfz 525|0.193|25|1.464|85 1010|0.223|25|0.572|85 0.02 Hgm 3580.01 Mh 2.4 Lck 4 Hhh 595|0.296|25|1.496|85 628|0.357|25|1.994|85649|0.379|25|2.119|85 359 0.0045 Mq 0.0137 Lu 0.21 Hfz500|0.153|25|0.933|85 740|1.337|25|0.927|85 360 0.02 Mak 2.5 Lbg 0.06Hfc 583|0.173|25|1.018|85 645|0.118|25|0.83|85 970|0.061|25|0.357|85 0.1Hje 361 0.01 Mo 0.55 Lbg 0.16 Hgi 525|0.173|25|0.406|85568|0.078|25|0.466|85 0.04 Hiu 362 0.01 Mo 0.16 Lck 0.1 Hgi533|0.046|25|0.231|85 578|0.024|25|0.269|85 0.1 Hkf 363 0.02 Mak 1 Lbw0.2 Hfz 705|1.219|25|2.861|85 756|1.217|25|2.746|85 364 0.01 Mo 2.4 Lbg0.02 Hfz 532|0.337|25|0.904|85 577|0.275|25|1.274|85 0.15 Hgh 365 0.02Mal 0.14 Lck 0.2 Hfz 496|0.164|25|1.644|85 556|0.188|25|0.823|85954|0.155|25|0.638|85 0.04 Hgx 366 0.02 Mak 1.05 Lc 0.2 Hfz662|0.385|25|1.917|85 704|0.539|25|2.1|85 755|0.511|25|1.911|85 3670.005 Mo 0.27 Lbg 0.35 Hgi 608|0.144|25|0.88|85 648|0.144|25|0.949|85777|0.182|25|1.029|85 0.15 Hjg 368 0.01 Mo 2.6 Lbg 0.04 Hfz534|0.324|25|0.916|85 590|0.221|25|1.232|85 0.15 Hgh 369 0.02 Mal 0.89Lbs 0.08 Hje 621|0.058|25|1.439|85 653|0.091|25|1.48|85704|0.115|25|1.515|85 370 0.003 Mal 0.065 Lck 0.03 Hir418|0.061|25|2.127|85 563|0.026|25|0.925|85 745|0.014|25|0.241|85 0.03Hjr 371 0.01 Mo 1.52 Lck 0.08 Hil 554|0.098|25|1.562|85589|0.102|25|2.1|85 638|0.111|25|2.528|85 372 0.02 Mal 0.18 Lck 0.01 Hbu515|0.041|25|0.813|85 689|0.161|25|1.269|85 744|0.119|25|1.237|85 0.2Hfz 0.02 Hje 373 0.002 Mo 0.022 Lck 0.2 Hir 508|0.05|25|2.194|85781|2.785|25|2.71|85 884|0.003|25|0.274|85 0.002 Mal 374 0.02 Mak 0.4Lbg 0.1 Hfz 665|0.145|25|0.663|85 705|0.164|25|0.763|85755|0.131|25|0.71|85 0.02 Hec 375 0.02 Mal 0.69 Lck 0.3 Hje617|0.055|25|1.144|85 654|0.087|25|1.779|85 704|0.093|25|1.796|85 3760.02 Mal 0.15 Lck 0.2 Hcn 670|0.226|25|0.743|85 377 0.02 Mak 5.2 Lbg0.16 Hfo 415|0.959|25|5|85 590|0.094|25|0.364|85 872|0.051|25|0.283|850.16 Hfz 378 0.02 Mal 0.12 Lck 0.005 Hdp 521|0.201|25|5|85707|0.141|25|1.589|85 875|0.062|25|0.223|85 0.2 Hir 379 0.01 Mo 0.33 Lbg0.35 Hgi 609|0.247|25|1.746|85 649|0.248|25|1.869|85776|0.312|25|1.974|85 0.15 Hjg 380 0.002 Mo 0.086 Lck 0.2 Hir561|0.143|25|1.562|85 724|1.26|25|1.575|85 778|2.266|25|2.519|85 0.002Mal 0.02 Hke 381 0.02 Mal 0.38 Lck 0.2 Hja 618|0.283|25|2.15|85666|0.359|25|1.963|85 1014|0.155|25|0.488|85 382 0.01 Mo 2.1 Lbg 0.069Hiu 535|0.213|25|0.591|85 567|0.179|25|0.68|85 0.066 Hjx 383 0.02 Mak0.2 Lm 0.2 Hfz 669|0.125|25|1.477|85 705|0.151|25|1.876|85757|0.129|25|1.828|85 0.16 Lck 384 0.02 Mak 2.3 Lbg 0.04 Hfo588|0.231|25|1.387|85 647|0.208|25|1.357|85 1050|0.115|25|0.544|85 0.2Hje 385 0.02 Mal 0.041 Lck 0.02 Hra 551|0.345|25|2.741|85936|0.097|25|0.648|85 1017|0.111|25|0.729|85 0.04 Hir 386 0.02 Mal 0.13Lck 0.1 Hrc 581|0.42|25|2.247|85 641|0.588|25|1.881|851005|0.113|25|0.791|85 0.06 Hij 387 0.02 Mal 0.15 Lck 0.2 Hfz500|0.186|25|1.101|85 563|0.239|25|0.574|85 757|0.176|25|0.715|85 0.02Hgt 388 0.02 Mak 0.041 Laz 0.2 Hfz 705|0.488|25|2.129|85757|0.461|25|2.088|85 389 0.02 Mak 0.47 Le 0.2 Hfz 705|0.24|25|2.912|85757|0.226|25|2.837|85 390 0.02 Mal 0.1 Hgz 502|0.049|25|0.539|85694|0.089|25|0.767|85 1020|0.167|25|0.48|85 0.4 Hij 0.069 Hke 391 0.02Mak 0.71 Lac 0.2 Hfz 663|0.081|25|1.853|85 703|0.095|25|2.176|85755|0.081|25|2.05|85 392 0.02 Man 0.33 Lck 0.1 Hfz 560|0.168|45|0.978|85635|0.248|45|1.232|85 984|0.088|45|0.413|85 0.25 Hhh 393 0.02 Mal 0.24Lck 0.02 Hdp 504|0.046|25|0.52|85 631|0.352|25|2.164|851129|0.1|25|0.52|85 0.2 Hfz 0.01 Hgz 394 0.02 Mal 0.33 Lck 0.02 Hdj650|0.116|25|1.222|85 756|0.052|25|0.347|85 0.21 Hfz 395 0.02 Mak 0.53Lcj 0.2 Hfz 663|0.48|25|2.113|85 703|0.626|25|2.259|85755|0.614|25|2.121|85 396 0.02 Mal 0.11 Lck 0.14 Hcz668|0.185|25|0.544|85 700|0.186|25|0.571|85 750|0.128|25|0.476|85 0.1Hfz 397 0.01 Mal 0.064 Lck 0.01 Hdp 460|0.233|25|5|85 521|0.127|25|5|85700|0.068|25|1.603|85 0.1 Hir 398 0.02 Mal 0.23 Lck 0.003 Hbt530|0.136|25|0.861|85 660|0.206|25|0.751|85 757|0.082|25|0.635|85 0.2Hfz 0.008 Hbb 399 0.003 Mal 0.12 Lck 0.03 Hir 416|0.075|25|1.589|85559|0.037|25|0.649|85 744|0.014|25|0.167|85 0.03 Hju 400 0.02 Mak 0.36Lbh 0.2 Hfz 668|0.144|25|1.607|85 704|0.196|25|1.964|85757|0.183|25|1.896|85 401 0.02 Mal 0.26 Lck 0.1 Hee 404|0.16|25|0.087|85653|0.094|25|1.612|85 705|0.099|25|1.632|85 402 0.02 Man 0.26 Lck 0.28Hds 650|0.14|25|0.456|85 0.2 Hfz 403 0.02 Mal 0.6 Lck 0.2 Hcn398|0.455|25|5|85 647|0.082|25|1.526|85 700|0.088|25|1.522|85 0.08 Hik404 0.02 Mal 0.069 Lck 0.2 Hcs 378|0.287|25|3.703|85654|0.066|25|0.564|85 721|0.06|25|0.485|85 0.04 Hfz 405 0.02 Mal 0.12Lck 0.1 Hbj 605|0.035|25|0.598|85 662|0.057|25|1.134|85754|0.043|25|1.135|85 0.1 Hij 406 0.01 Mh 0.03 Lu 0.97 Hfz518|0.619|25|0.411|85 701|0.25|25|3.312|85 724|0.281|25|3.888|85 4070.02 Mal 0.26 Lck 0.04 Hfd 643|0.149|25|1.19|85 693|0.152|25|1.302|85750|0.079|25|0.742|85 0.2 Hij 408 0.01 Mo 2.21 Lck 0.05 Hes594|0.173|25|1.61|85 663|0.146|25|1.799|85 694|0.16|25|1.967|85 0.1 Hke409 0.02 Mak 0.94 Lah 0.2 Hfz 665|0.334|25|2.266|85704|0.461|25|2.626|85 754|0.445|25|2.468|85 410 0.01 Me 1.23 Lbs 0.3 Hke433|1.477|25|5|45 615|0.081|25|0.771|85 922|0.072|25|0.658|85 411 0.02Mak 0.16 Lck 0.2 Hfz 704|0.139|25|1.824|85 756|0.117|25|1.765|85 4120.01 Mo 0.13 Lck 0.034 Hhj 602|0.13|25|1.139|85 622|0.113|25|1.123|85661|0.093|25|1.01|85 413 0.02 Mal 0.45 Lck 0.01 Hea500|0.117|25|1.096|85 640|0.257|25|0.913|85 995|0.139|25|0.627|85 0.4Hfz 0.12 Hhh 414 0.01 Mo 1.68 Lck 0.02 Hbu 596|0.109|25|1.705|85646|0.127|25|2.929|85 0.1 Hfz 415 0.01 Mo 1 Lck 0.1 Hfz641|0.06|25|1.451|85 669|0.093|25|2.223|85 700|0.132|25|3.402|85 4160.02 Mak 0.37 Lbg 0.08 Hfw 533|0.112|25|3.621|85 738|0.19|25|0.931|850.2 Hir 417 0.02 Mak 1.04 Li 0.2 Hfz 665|0.676|25|2.34|85706|0.879|25|2.641|85 755|0.829|25|2.413|85 418 0.02 Mal 0.31 Lck 0.1Har 578|0.139|25|2.143|85 624|0.245|25|1.795|85 990|0.074|25|0.592|850.06 Hij 419 0.02 Mak 0.47 Lae 0.2 Hfz 667|0.168|25|2.305|85704|0.233|25|2.812|85 756|0.214|25|2.67|85 420 0.04 Mal 0.41 Lck 0.02Hbs 485|0.035|25|0.999|85 652|0.248|25|1.824|85 704|0.206|25|1.759|850.2 Hje 421 0.02 Mal 0.14 Lck 0.01 Hew 503|0.032|25|0.191|85703|0.291|25|1.917|85 757|0.257|25|1.877|85 0.2 Hfz 422 0.02 Man 0.14Lck 0.04 Hbs 486|0|25|0.45|85 829|0|25|0.192|85 939|0|25|0.277|85 0.1Hje 423 0.02 Mal 0.33 Lck 0.01 Hbt 529|0.048|25|0.719|85630|0.152|25|0.593|85 973|0.076|25|0.37|85 0.01 Hbu 0.2 Hfz 424 0.02 Mal0.18 Lck 0.2 Hfz 522|0.101|25|1.025|85 703|0.193|25|1.05|85757|0.136|25|1.043|85 0.01 Hbb 425 0.01 Mo 1.29 Lck 0.06 Hit552|0.115|25|1.428|85 590|0.12|25|1.969|85 637|0.129|25|2.269|85 4260.02 Mak 0.3 Lbg 0.04 Hhl 506|0.056|25|2.086|85 815|0.057|25|0.38|85 0.2Hir 427 0.02 Mal 0.52 Lck 0.02 Hr 555|0.035|25|0.346|85621|0.088|25|0.502|85 695|0.079|25|0.281|85 0.1 Hij 428 0.02 Mak 0.13Lch 0.2 Hfz 671|0.354|25|2.247|85 704|0.504|25|2.896|85757|0.491|25|2.823|85 429 0.02 Mal 0.55 Lck 0.2 Hje653|0.085|25|1.419|85 704|0.087|25|1.429|85 430 0.01 Mo 0.062 Lck 0.1Hgi 534|0.099|25|0.547|85 579|0.116|25|0.737|85 610|0.13|25|0.654|85 0.1Hkf 431 0.02 Mal 0.35 Lck 0.12 Hfd 639|0.167|25|1.417|85676|0.156|25|1.369|85 1030|0.112|25|0.649|85 0.21 Hij 432 0.02 Mal 0.23Lck 0.02 Hbt 565|0.093|25|1.374|85 650|0.116|25|1.081|85 0.02 Hfz 0.2Hir 433 0.01 Mo 3.3 Lck 1 Hdp 597|0.101|25|1.829|85647|0.135|25|3.039|85 0.1 Hfz 434 0.02 Mak 0.18 Lbg 0.01 Hfz780|0.161|25|1.04|85 0.01 Hga 0.2 Hir 435 0.01 Mo 0.48 Lck 0.35 Hgi569|0.091|25|0.862|85 648|0.164|25|2.027|85 687|0.105|25|1.42|85 0.1 Hhh0.15 Hjg 436 0.003 Mal 0.082 Lck 0.03 Hir 418|0.168|25|5|85561|0.076|25|1.922|85 745|0.022|25|0.475|85 0.09 Hke 437 0.02 Mak 0.31Lcl 0.2 Hfz 663|0.302|25|2.372|85 704|0.443|25|3.065|85756|0.429|25|2.96|85 438 0.02 Mak 0.21 Lbg 0.33 Hir502|0.201|25|1.582|85 820|0.118|25|0.347|85 0.062 Hiu 439 0.01 Mo 1.23Lck 0.1 Hio 549|0.133|25|1.098|85 589|0.132|25|1.531|85636|0.138|25|1.724|85 440 0.02 Mak 0.57 La 0.2 Hfz 662|0.081|25|1.811|85703|0.115|25|2.258|85 756|0.097|25|2.132|85 441 0.11 Eg 0.06 Hdy568|0.087|25|0.465|85 655|0.098|25|0.853|85 0.005 Mo 0.011 Hje 442 0.02Mal 0.12 Lck 0.01 Hdp 521|0.171|25|5|85 704|0.095|25|2.402|851191|0.08|25|0.503|85 0.2 Hjg 443 0.003 Mal 0.055 Lck 0.006 Hfo410|0.106|25|0.878|85 500|0.046|25|0.398|85 555|0.042|25|0.367|85 0.03Hir 444 0.02 Mak 0.15 Lci 0.2 Hfz 705|0.435|25|3.022|85754|0.416|25|2.925|85 445 0.02 Mak 1 Lbg 0.02 Hea 498|0.107|25|1.238|85880|0.097|25|0.366|85 997|0.148|25|0.532|85 0.16 Hfz 446 0.011 Mak 0.79Lbg 0.046 Hfz 560|0.026|25|0.602|85 634|0.127|25|0.758|85978|0.037|25|0.261|85 0.25 Hhh 447 0.009 Mak 1.5 Lbg 0.11 Hfz370|0.663|25|5|85 640|0.068|25|0.495|85 696|0.071|25|0.45|85 0.052 Hjy448 0.01 Mal 0.11 Lck 0.03 Har 443|0.115|25|5|85 512|0.028|25|1.679|85602|0.114|25|1.302|85 0.005 Hff 0.1 Hir 449 0.02 Mak 0.68 Lbg 0.02 Hfw650|0.142|25|1.207|85 693|0.176|25|1.134|85 1205|0.116|25|0.288|85 0.1Hfz 450 0.02 Mal 0.11 Lck 0.2 Hfz 496|0.24|25|1.986|85555|0.18|25|0.98|85 757|0.256|25|0.98|85 0.02 Hgx 451 0.02 Mak 0.59 Laj0.2 Hfz 668|0.268|25|2.396|85 705|0.36|25|2.844|85 755|0.344|25|2.693|85452 0.02 Mal 0.02 Lav 0.4 Hfz 328|0.894|25|3.022|85704|0.248|25|0.477|85 756|0.223|25|0.454|85 453 0.01 Mal 0.21 Lck 0.04Hfz 377|0.388|25|5|85 446|0.142|25|2.831|85 680|0.058|25|0.64|85 0.1 Hir0.01 Hke 454 0.02 Mak 0.47 Lck 0.2 Hes 653|0.077|25|1.741|85705|0.082|25|1.744|85 455 0.003 Mal 0.054 Lck 0.03 Hir418|0.097|25|2.535|85 562|0.046|25|1.094|85 745|0.019|25|0.282|85 0.012Hke 456 0.02 Mal 0.28 Lck 0.02 Hbu 521|0.034|25|1.118|85860|0.048|25|0.355|85 970|0.072|25|0.474|85 0.2 Hfz 457 0.01 Mi 0.03 Lu0.1 Hga 501|0.49|25|0.317|85 634|0.274|25|1.313|85 695|0.413|25|2.282|85458 0.01 Mo 2.34 Lck 0.1 Hes 592|0.052|25|0.861|85 667|0.133|25|2.307|85692|0.146|25|2.592|85 459 0.02 Mal 0.37 Lck 0.04 Hbt521|0.167|25|0.756|85 613|0.185|25|1.082|85 698|0.096|25|0.524|85 0.1Hje 460 0.01 Mo 0.94 Lck 0.04 Hgh 548|0.153|25|0.671|85587|0.103|25|0.573|85 0.1 Hhh 461 0.01 Mo 1.7 Lck 0.02 Hfz538|0.335|25|0.674|85 610|0.292|25|0.843|85 652|0.27|25|0.823|85 0.1 Hjy462 0.02 Mal 0.3 Lck 0.04 Hdh 570|0.197|25|1.752|85610|0.283|25|2.127|85 1121|0.118|25|0.512|85 0.1 Hje 463 0.01 Mo 0.71Lck 0.04 Hfj 535|0.017|25|0.353|85 585|0.005|25|0.379|85631|0.002|25|0.335|85 464 0.02 Mal 0.06 Lck 0.06 Hij659|0.09|25|1.078|85 705|0.117|25|1.223|85 754|0.1|25|1.175|85 465 0.02Mal 0.29 Lck 0.1 Hah 576|0.154|25|2.084|85 846|0.057|25|0.238|85993|0.094|25|0.605|85 0.06 Hij 466 0.02 Mal 0.16 Lck 0.02 Hbu519|0.106|25|1.749|85 853|0.072|25|0.542|85 968|0.102|25|0.723|85 0.2Hfz 467 0.002 Mak 0.07 Lbm 0.32 Hjg 506|0|25|0.698|85 856|0|25|0.103|85468 0.02 Mal 0.28 Lck 0.2 Hfz 519|0.118|25|1.628|85870|0.064|25|0.345|85 1010|0.115|25|0.667|85 0.02 Hgm 0.02 Hje 469 0.04Mal 0.46 Lck 0.013 Hbt 483|0.095|25|0.901|85 652|0.2|25|1.636|85704|0.198|25|1.496|85 0.013 Hea 0.2 Hje 470 0.01 Mo 0.23 Lck 0.36 Hcx547|0.146|25|0.639|85 0.1 Hiu 471 0.02 Mal 0.064 Lck 0.02 Hbf496|0.113|25|1.402|85 758|0.194|25|0.573|85 991|0.101|25|0.47|85 0.2 Hij472 0.02 Mal 0.59 Lck 0.02 Hrb 557|0.185|25|1.642|85595|0.265|25|1.913|85 1010|0.123|25|0.701|85 0.08 Hij 473 0.02 Mal 0.14Lck 0.2 Hfz 502|0.143|25|1.583|85 560|0.138|25|0.703|85757|0.2|25|0.91|85 0.02 Hgw 474 0.01 Mal 0.49 Ly 0.02 Hv410|0.072|25|0.411|85 503|0.056|25|1.174|85 475 0.02 Mal 0.29 Lck 0.0405Haj 553|0.084|25|1.417|85 608|0.172|25|1.749|85 1000|0.073|25|0.425|850.06 Hij 476 0.02 Mal 2 Lbs 0.0402 Haj 590|0.099|25|1.646|85629|0.139|25|1.389|85 990|0.089|25|0.473|85 0.06 Hij 477 0.01 Mal 0.22Lck 0.07 Hij 640|0.117|25|1.213|85 676|0.112|25|1.154|851030|0.068|25|0.553|85 0.07 Hke 478 0.02 Mal 1 Lbg 0.0402 Haj560|0.091|25|1.691|85 608|0.183|25|1.932|85 988|0.091|25|0.494|85 0.06Hij 479 0.005 Mf 0.072 Lck 0.04 Hir 417|0.161|25|3.369|85562|0.072|25|1.427|85 745|0.023|25|0.359|85 480 0.007 Maj 0.128 Lck 0.07Hir 416|0.215|25|5|85 562|0.096|25|2.567|85 745|0.035|25|0.639|85 0.035Hke 481 0.01 Mal 0.35 Lbg 0.02 Hv 409|0.08|25|0.471|85505|0.06|25|1.308|85 482 0.01 Mal 0.65 Lbs 0.02 Hv 408|0.069|25|0.455|85503|0.042|25|1.351|85 483 0.02 Mal 0.35 Lck 0.1 Hay 575|0.1|25|1.933|85618|0.207|25|1.634|85 990|0.066|25|0.544|85 0.06 Hij 484 0.01 Mal 1.19Lcs 0.02 Hv 408|0.063|25|0.822|85 504|0.05|25|2.629|85 485 0.02 Mal 0.61Lbs 0.02 Hv 408|0.115|25|0.616|85 503|0.033|25|1.63|85 0.47 Lcs 486 0.01Mal 0.16 Lao 0.02 Hv 409|0.058|25|0.295|85 503|0.028|25|0.808|85 4870.005 Mal 0.27 Lbs 0.01 Hv 408|0.058|25|0.386|85 503|0.127|25|1.239|85488 0.005 Mal 0.28 Lbg 0.01 Hv 408|0.033|25|0.224|85503|0.028|25|0.664|85 489 0.01 Mal 0.0401 Lck 0.02 Hv405|0.063|25|0.313|85 503|0.115|25|0.976|85 490 0.005 Mf 0.07 Lck 0.04Hir 417|0.103|25|2.619|85 561|0.045|25|1.125|85 745|0.016|25|0.29|85 4910.01 Mac 0.12 Lck 585|0.162|25|1.137|85 627|0.17|25|0.982|85994|0.057|25|0.298|85 492 0.01 Mac 0.12 Lck 586|0.175|25|0.857|65622|0.183|25|0.768|65 996|0.058|25|0.231|65 0.03 Lcs 493 0.0101 Mal 0.37Lck 0.01 Haj 639|0.182|25|1.573|85 679|0.157|25|1.41|851194|0.093|25|0.326|85 0.25 Hij 494 0.005 Mb 0.07 Lck 0.04 Hir405|0.17|25|2.215|85 498|0.071|25|1.088|85 539|0.056|25|0.871|85 4950.02 Mac 0.2 Lck 582|0.227|25|2.062|85 621|0.27|25|1.83|85995|0.096|25|0.559|85 496 0.02 Mal 0.61 Lbs 0.02 Hv408|0.135|25|0.772|85 504|0.092|25|2.172|85 497 0.01 Mo 0.85 Lck 0.2 Hfe620|0.069|25|1.38|85 680|0.134|25|2.591|85 703|0.154|25|2.929|85 0.04Hfz 498 0.02 Mal 0.354 Lck 0.1 Hc 580|0.114|25|1.758|85623|0.211|25|1.466|85 995|0.068|25|0.498|85 0.06 Hij 499 0.02 Mal 0.317Lck 0.1 Ham 577|0.106|25|1.701|85 625|0.234|25|1.426|85990|0.068|25|0.475|85 0.06 Hij 500 0.02 Mal 0.347 Lck 0.1 Haj578|0.117|25|1.83|85 625|0.215|25|1.547|85 993|0.069|25|0.509|85 0.06Hij 501 0.01 Mao 0.15 Lck 0.027 Hgm 491|0.497|25|1.5|851038|0.176|25|0.102|85 0.015 Mal 502 0.01 Mal 0.097 Lck 0.01 Ha530|0.065|25|0.442|85 702|0.058|25|0.783|85 755|0.047|25|0.739|85 0.08Hij 503 0.02 Mal 0.082 Lck 0.06 Ho 658|0.061|25|0.629|85704|0.062|25|0.694|85 753|0.048|25|0.641|85 0.06 Hij 504 0.02 Mal 0.34Lck 0.02 Hm 554|0.121|25|2.072|85 59|0.115|25|1.567|851032|0.083|25|0.602|85 0.06 Hij 505 0.02 Mal 0.077 Lck 0.02 Hm598|0.159|25|2.34|85 646|0.157|25|1.902|85 1057|0.08|25|0.519|85 0.16Hir 506 0.02 Mal 2 Lbs 0.0405 Haj 590|0.131|25|1.66|85626|0.166|25|1.454|85 986|0.099|25|0.478|85 0.06 Hij 507 0.02 Mal 0.66Lck 0.02 Hm 534|0.153|25|1.39|85 565|0.12|25|1.162|851010|0.089|25|0.486|85 0.04 Hje 508 0.01 Mal 3.3 Laq 0.2 Hij655|0.326|25|1.277|65 706|0.333|25|1.267|65 750|0.268|25|1.048|65 5090.02 Mal 0.47 Lbg 0.02 Hv 407|0.16|25|0.586|85 503|0.05|25|1.542|85 5100.02 Mal 0.094 Lci 0.02 Hv 408|0.1|25|0.554|85 503|0.138|25|1.581|85 5110.02 Mal 0.0784 Lch 0.02 Hv 408|0.084|25|0.442|85 504|0.109|25|1.249|85512 0.02 Mal 0.067 Lcg 0.02 Hv 408|0.076|25|0.378|85503|0.092|25|1.04|85 513 0.02 Mal 0.446 Lac 0.02 Hv408|0.166|25|0.895|85 503|0.153|25|2.595|85 514 0.02 Mal 0.44 Lt 0.02 Hv412|0.168|25|1|85 503|0.165|25|2.961|85 515 0.02 Mal 1.1 Lw 0.02 Hv414|0.372|25|1.361|85 503|0.356|25|3.871|85 516 0.02 Mal 0.33 Ly 0.02 Hv410|0.208|25|1.044|85 503|0.315|25|3.145|85 517 0.01 Mac 1 Lbs578|0.128|25|1.254|85 617|0.133|25|1.105|85 985|0.067|25|0.352|85 5180.02 Mal 0.038 Lck 0.16 Ho 555|0.12|25|0.669|85 600|0.121|25|0.567|85686|0.094|25|0.282|85 0.02 Hij 519 0.02 Mal 0.04 Lck 0.04 Hir529|0.174|25|4.758|85 773|0.053|25|0.803|85 847|0.033|25|0.7|85 0.2 Hka520 0.01 Mal 3.4 Laq 0.02 Hv 415|0.093|25|0.681|85 505|0.15|25|2.004|850.3 Lbs 521 0.02 Mal 0.027 Lck 0.02 Hak 515|0.038|25|0.16|85705|1.023|25|2.086|85 756|1.031|25|2.076|85 0.1 Hij 522 0.01 Mal 0.019Lbt 0.02 Hv 510|0.149|25|0.318|85 523 0.02 Mal 1.01 Lbg 0.0602 Haj586|0.161|25|2.455|85 847|0.034|25|0.248|85 985|0.103|25|0.687|85 0.06Hij 524 0.02 Mal 1.54 Lbs 0.0602 Haj 579|0.176|25|2.898|85845|0.032|25|0.282|85 988|0.125|25|0.817|85 0.06 Hij 525 0.02 Mal 1.5Lbs 0.061 Hat 560|0.073|25|1.671|85 600|0.111|25|1.799|85996|0.101|25|0.519|85 0.06 Hij 526 0.02 Mal 0.03 Lck 0.02 Hao522|0.065|25|0.348|85 657|0.15|25|0.628|85 753|0.106|25|0.566|85 0.04Hij 527 0.005 Mf 0.07 Lck 0.04 Hir 417|0.144|25|3.517|85562|0.064|25|1.535|85 745|0.023|25|0.388|85 528 0.02 Mal 0.2 Lck 0.04Has 545|0.088|25|1.568|85 603|0.232|25|2.185|85 967|0.069|25|0.539|850.1 Hij 529 0.02 Mal 0.078 Lck 0.04 Hcg 366|0.439|25|5|85645|0.189|25|1.001|85 692|0.181|25|0.982|85 0.08 Hij 530 0.02 Mal 0.21Lck 0.05 Hfr 593|0.321|25|2.967|85 998|0.121|25|0.689|85 0.06 Hij 5310.005 Mo 0.5 Lck 0.02 Hij 618|0.037|25|0.743|85 639|0.047|25|0.838|85702|0.1|25|1.855|85 532 0.02 Mal 0.063 Lck 0.08 Hk 523|0.062|25|0.171|85658|0.142|25|1.219|85 701|0.118|25|1.215|85 0.06 Hij 533 0.005 Mal 0.018Lck 0.015 Haj 390|0.12|25|1.602|85 440|0.018|25|1.226|85604|0.041|25|0.228|85 0.005 Hir 0.025 Hke 534 0.02 Mal 0.12 Lck 0.08 Hae668|0.082|25|0.821|85 705|0.08|25|0.876|85 745|0.059|25|0.713|85 0.08Hij 535 0.02 Mal 0.066 Lck 0.024 Heu 432|0.191|25|1.063|85718|0.089|25|0.339|85 0.061 Hij 536 0.02 Mal 0.84 Lbs 0.02 Heu430|0.163|25|0.916|85 704|0.11|25|0.329|85 0.08 Hij 537 0.02 Mal 0.11Lck 0.052 Hfs 543|0.118|25|1.241|85 601|0.258|25|1.697|85970|0.087|25|0.44|85 0.061 Hij 538 0.005 Mf 0.07 Lck 0.04 Hhv418|0.105|25|2.972|85 563|0.052|25|1.309|85 745|0.018|25|0.327|85 5390.02 Mal 0.12 Lck 0.024 Hhb 435|0.967|25|2.949|85 717|0.301|25|0.877|850.06 Hij 540 0.01 Me 0.24 Lck 0.3 Hke 432|0.952|25|4.559|65632|0.118|25|0.692|85 944|0.065|25|0.366|85 541 0.02 Mal 0.078 Lck 0.05Hau 547|0.073|25|1.188|85 607|0.242|25|1.837|85 978|0.079|25|0.424|850.06 Hij 542 0.01 Mal 0.9 Lbs 0.02 Hai 360|0.175|25|5|85636|0.057|25|0.993|85 689|0.059|25|0.757|85 0.04 Hij 543 0.01 Mal 0.051Lck 0.02 Hbl 532|0.168|25|2.041|85 602|0.094|25|0.882|85929|0.048|25|0.547|85 0.04 Hir 544 0.01 Mal 0.38 Lae 0.02 Hv408|0.085|25|0.525|85 503|0.086|25|1.597|85 545 0.01 Mal 0.42 Lk 0.02 Hv408|0.069|25|0.331|85 503|0.036|25|0.94|85 546 0.01 Mal 0.034 Lbl 0.2Hij 706|0.566|25|1.358|85 757|0.576|25|1.323|85 547 0.01 Mal 0.32 Lbh0.02 Hv 404|0.075|25|0.241|85 503|0.022|25|0.61|85 548 0.01 Mal 0.53 Lh0.02 Hv 404|0.067|25|0.264|85 503|0.021|25|0.726|85 549 0.02 Mal 0.087Lck 0.04 Hx 465|0.255|25|0.684|85 633|0.128|25|0.332|85750|0.125|25|0.263|85 0.05 Hij 550 0.01 Mal 0.26 Lck 0.01 Haj615|0.103|25|0.9|85 664|0.094|25|0.723|85 0.03 Hij 0.021 Hje 551 0.01Mal 0.72 Lbs 0.01 Hai 361|0.29|25|5|85 642|0.071|25|0.827|85696|0.069|25|0.617|85 0.041 Hij 552 0.02 Mal 0.21 Lck 0.02 Haj621|0.182|25|1.511|85 937|0.07|25|0.618|85 1022|0.089|25|0.607|85 0.04Hij 0.4 Hke 553 0.005 Mo 0.95 Lck 0.08 Hij 618|0.024|25|0.697|85668|0.051|25|1.496|85 701|0.071|25|2.299|85 554 0.01 Mal 3.68 Laq 0.02Hv 418|0.295|25|0.691|85 504|0.928|25|2.072|85 0.01 Lck 555 0.01 Mal5.62 Lbo 0.02 Hv 406|0.076|25|0|85 503|0.038|25|0|85 556 0.01 Mal 0.032Lq 0.02 Hv 405|0.207|25|0.43|85 501|0.13|25|0.656|85 557 0.005 Mo 0.54Lck 0.025 Hij 618|0.038|25|0.78|85 640|0.049|25|0.899|85701|0.102|25|2.025|85 558 0.005 Mo 0.6 Lck 0.03 Hij618|0.038|25|0.779|85 640|0.047|25|0.918|85 701|0.099|25|2.088|85 5590.02 Mal 0.15 Lck 0.081 Hx 467|0.393|25|0.986|85 580|0.109|25|0.464|85750|0.164|25|0.33|85 0.1 Hij 560 0.01 Mal 0.097 Lck 0.021 Ha527|0.148|25|0.661|85 700|0.08|25|0.747|85 754|0.068|25|0.68|85 0.083Hij 561 0.02 Mal 0.099 Lck 0.045 Hat 558|0.157|25|1.366|85615|0.25|25|1.868|85 1016|0.084|25|0.407|85 0.042 Hij 562 0.01 Mo 1 Lck0.04 Haj 548|0.417|25|1.042|85 0.04 Hiu 563 0.01 Mal 1.16 Lcc 0.02 Hv504|0.043|25|0.723|85 564 0.005 Mo 0.7 Lck 0.041 Hij618|0.03|25|0.761|85 671|0.06|25|1.425|85 700|0.084|25|2.157|85 565 0.02Mal 1.21 Lck 0.02 Hdy 503|0.156|25|1.349|85 883|0.05|25|0.333|85991|0.081|25|0.548|85 0.2 Hfz 566 0.02 Mak 0.13 Lbv 0.2 Hfz353|1.034|25|5|65 704|0.18|25|1.753|85 757|0.158|25|1.698|85 567 0.02Mak 0.2 Lbg 0.03 Hfz 745|0.246|25|1.65|85 0.01 Hga 0.2 Hir 568 0.02 Mak0.13 Lck 0.2 Hfz 354|0.683|25|5|65 704|0.128|25|2.066|85756|0.103|25|1.993|85 569 0.002 Mo 0.43 Lck 0.02 Hfo393|0.05|25|0.847|85 441|0.044|25|0.859|85 746|0.01|25|0.412|85 0.02 Hir570 0.017 Mal 0.295 Lck 0.39 Hij 542|0.027|25|0.114|85706|0.367|25|2.943|85 757|0.367|25|2.92|85 571 0.02 Mal 0.28 Lck 0.1 Hes403|0.155|25|0.101|85 654|0.079|25|1.247|85 704|0.083|25|1.252|85 5720.01 Mo 1.1 Lbg 0.064 Hgh 528|0.311|25|0.682|85 574|0.211|25|0.854|85573 0.02 Mal 0.25 Lck 0.16 Hac 576|0.151|25|0.529|85645|0.168|25|0.543|85 0.04 Hik 574 0.01 Mal 0.381 Lbh 0.2 Hij353|0.38|25|5|55 705|0.084|25|1.546|85 757|0.08|25|1.536|85 575 0.02 Mak0.48 Lbg 0.04 Hfz 585|0.127|25|1.443|85 650|0.313|25|1.543|85989|0.066|25|0.465|85 0.12 Hhh 0.2 Hir 576 0.01 Mo 0.079 Lav 0.1 Hfz562|0.42|25|0.425|85 665|0.156|25|0.835|85 725|0.188|25|1.249|85 5770.02 Mak 0.52 Ly 0.2 Hfz 669|0.259|25|2.665|85 703|0.337|25|3.312|85755|0.315|25|3.132|85 578 0.01 Mal 0.27 Lck 0.1 Hir413|0.124|25|2.277|85 590|0.033|25|0.407|85 650|0.047|25|0.49|85 0.02Hje 0.02 Hke 579 0.02 Mal 2.09 Lbs 0.1 Har 570|0.11|25|1.948|85627|0.171|25|1.558|85 984|0.099|25|0.58|85 0.06 Hij 580 0.02 Mal 1.38Lck 0.0057 Hs 400|2.04|25|1.413|85 493|0.851|25|0.266|85 0.2 Hij 5810.002 Mak 0.32 Hir 374|1.837|25|5|85 500|0.418|25|1.755|85780|0.143|25|0.375|85 0.012 Hjx 582 0.002 Mal 0.006 Lck 0.02 Hir385|0.472|25|2.007|85 506|0.013|25|0.695|85 723|0.01|25|0.189|85 0.1 Hkf583 0.02 Mal 0.51 Lck 0.2 Hje 654|0.081|25|1.607|85704|0.085|25|1.623|85 584 0.02 Mak 0.8 Lbg 0.06 Hfw652|0.137|25|1.229|85 694|0.167|25|1.135|85 1205|0.117|25|0.306|85 0.1Hfz 585 0.02 Mak 0.8 Lap 0.2 Hfz 667|0.126|25|1.682|85703|0.186|25|1.966|85 756|0.18|25|1.864|85 586 0.02 Mak 0.13 Lch 0.2 Hfz669|0.336|25|2.283|85 704|0.474|25|2.914|85 757|0.458|25|2.837|85 5870.02 Mal 0.36 Lck 0.2 Hfz 513|0.377|25|2.22|85 640|0.195|25|0.568|85957|0.159|25|0.777|85 0.02 Hgu 588 0.02 Mal 0.26 Lck 0.1 Hab591|0.22|25|1.285|85 648|0.248|25|1.134|85 1027|0.109|25|0.348|85 0.06Hij 589 0.02 Mal 0.14 Lck 0.07 Hha 534|0.093|25|0.303|85704|0.193|25|1.075|85 756|0.177|25|1.056|85 0.2 Hfz 590 0.02 Mal 0.086Lck 0.04 Har 511|0.096|25|5|85 602|0.185|25|2.824|85660|0.225|25|2.649|85 0.1 Hir 591 0.02 Mal 0.21 Lck 0.2 Hfz521|0.082|25|1.318|85 850|0.065|25|0.524|85 953|0.095|25|0.574|85 0.02Hbb 592 0.02 Mak 0.25 Lb 0.2 Hfz 704|0.391|25|3.312|85757|0.376|25|3.136|85 593 0.02 Mal 0.1 Lck 0.1 Hy 669|0.097|25|0.979|85704|0.096|25|1.155|85 756|0.074|25|1.112|85 0.09 Hfz 594 0.02 Mal 0.1Lck 0.09 Hfz 670|0.007|25|0.799|85 704|0.017|25|0.955|85756|0.008|25|0.923|85 0.1 Hhd 595 0.01 Mo 2.28 Lck 0.02 Hbt594|0.205|25|2.035|85 644|0.357|25|3.633|85 1082|0.044|25|0.282|85 0.1Hfz 596 0.01 Mo 0.5 Lck 0.1 Hfz 586|0.187|25|0.92|85655|0.184|25|1.596|85 0.02 Hbf 597 0.01 Mo 1.52 Lck 0.08 Hil554|0.132|25|1.594|85 607|0.155|25|2.294|85 637|0.172|25|2.565|85 0.045Hiu 598 0.0052 Mo 1.3 Lck 0.04 Hil 554|0.043|25|0.827|85590|0.041|25|1.104|85 637|0.043|25|1.31|85 0.04 Hhj 0.04 Hik 599 0.005Mo 0.28 Lck 0.02 Hnr 525|0.297|25|2.396|85 724|3.305|25|3.227|85996|0.183|25|0.908|85 0.02 Mal 0.2 Hij 600 0.01 Mo 1.52 Lck 0.1 Hfz586|0.178|25|1.428|85 630|0.262|25|2.428|85 0.01 Hbb 601 0.02 Mal 0.17Lck 0.2 Hfz 526|0.25|25|1.567|85 760|0.103|25|0.353|85966|0.124|25|0.595|85 0.02 Haz 602 0.02 Mak 0.85 Lbu 0.2 Hfz667|0.423|25|1.951|85 705|0.623|25|2.39|85 755|0.62|25|2.252|85 603 0.01Mo 1.3 Lbg 0.009 Hgc 546|0.194|25|0.346|85 588|0.17|25|0.47|85632|0.16|25|0.48|85 604 0.01 Mo 4.67 Lbg 0.1 Hbz 593|0.143|25|0.71|85681|0.142|25|1.106|85 0.038 Hje 605 0.005 Mal 0.034 Lck 0.015 Hhc530|0.15|25|1.195|85 694|0.029|25|0.237|85 606 0.02 Mal 0.94 Lbs 0.1 Hje620|0.081|25|1.639|85 653|0.121|25|1.857|85 704|0.144|25|1.894|85 6070.02 Mak 0.28 Lbg 0.117 Hfz 667|0.172|25|1.56|85 705|0.237|25|1.842|85756|0.216|25|1.733|85 0.071 Hhl 608 0.02 Mak 1.1 Lbg 0.04 Hcb620|0.229|25|1.563|85 649|0.246|25|1.451|85 0.1 Hje 609 0.01 Mo 2.1 Lbg0.033 Hiu 534|0.178|25|0.499|85 570|0.131|25|0.571|85 0.066 Hjx 610 0.01Mal 0.503 Lao 0.2 Hij 353|0.195|25|5|85 704|0.045|25|1.165|85756|0.035|25|1.13|85 611 0.02 Mal 0.14 Lck 0.2 Hha 531|0.149|25|0.466|85703|0.164|25|0.744|85 757|0.152|25|0.736|85 0.2 Hfz 612 0.02 Mal 0.18Lck 0.04 Hbl 503|0.17|25|1.783|85 658|0.08|25|0.528|85984|0.084|25|0.65|85 0.1 Hij 613 0.02 Mal 0.16 Lck 0.02 Hbl504|0.169|25|0.804|85 705|0.214|25|2.173|85 757|0.202|25|2.14|85 0.2 Hij614 0.02 Mal 0.16 Lck 0.02 Hbl 504|0.12|25|1.009|85704|0.085|25|1.247|85 756|0.069|25|1.202|85 0.15 Hij 615 0.02 Mal 0.32Lck 0.02 Hrc 558|0.053|25|0.623|85 617|0.09|25|0.832|85702|0.098|25|0.749|85 0.08 Hje 616 0.02 Mal 0.4 Lck 0.1 Hav589|0.112|25|0.75|85 648|0.177|25|0.636|85 1032|0.083|25|0.227|85 0.06Hij 617 0.02 Mal 0.49 Lck 0.1 Hab 591|0.081|25|0.645|85650|0.138|25|0.567|85 1038|0.075|25|0.2|85 0.06 Hij 618 0.01 Mal 0.598Lbg 0.2 Hij 667|0.065|25|1.259|85 705|0.089|25|1.748|85757|0.083|25|1.722|85 619 0.01 Mo 0.86 Lck 0.04 Hbl573|0.227|25|1.584|85 633|0.316|25|2.775|85 699|0.07|25|1.287|85 0.04Hij 620 0.0202 Mal 0.933 Lck 1.034 Hij 673|0.105|25|1.841|85706|0.123|25|2.41|85 757|0.11|25|2.401|85 621 0.01 Mal 0.1 Laz 0.2 Hij668|0.085|25|0.472|85 703|0.095|25|0.642|85 756|0.08|25|0.634|85 6220.02 Mal 0.349 Lck 0.395 Hij 670|0.119|25|1.872|85 707|0.152|25|2.612|85757|0.14|25|2.601|85 623 0.02 Mal 0.099 Lck 0.1 Haq664|0.104|25|1.169|85 705|0.093|25|1.205|85 750|0.069|25|1.012|85 0.082Hij 624 0.01 Mal 0.0492 Lck 0.04 Hij 658|0.036|25|0.548|85705|0.042|25|0.635|85 754|0.035|25|0.609|85 625 0.01 Mal 0.0303 Lck0.0304 Hij 654|0.061|25|0.671|85 707|0.084|25|0.649|85753|0.074|25|0.615|85 626 0.01 Mal 0.154 Lck 0.2 Hij669|0.101|25|1.154|85 705|0.141|25|1.606|85 757|0.138|25|1.606|85 6270.01 Mal 0.0399 Laz 0.2 Hij 353|0.098|25|3.282|85 704|0.064|25|0.396|85757|0.049|25|0.381|85 0.437 Lbs 628 0.01 Mal 0.694 Ly 0.2 Hij669|0.074|25|1.429|85 705|0.095|25|1.907|85 756|0.088|25|1.879|85 6290.01 Mal 2 Lcs 0.2 Hij 667|0.028|25|0.899|65 706|0.031|25|1.258|65756|0.027|25|1.215|65 630 0.02 Mal 0.324 Lck 0.1 Hdt577|0.119|25|2.009|85 625|0.261|25|1.681|85 989|0.067|25|0.551|85 0.06Hij 631 0.02 Mal 2.35 Lcs 0.1 Hdt 575|0.139|25|2.067|65625|0.198|25|1.688|65 982|0.081|25|0.56|65 0.06 Hij 632 0.02 Mal 0.064Lck 0.04 Hbn 530|0.308|25|1.322|85 705|0.234|25|1.338|85756|0.213|25|1.256|85 0.08 Hij 633 0.01 Mh 1.4 Lck 0.1 Hij566|0.189|25|1.598|85 589|0.221|25|1.982|85 634|0.273|25|2.523|85 0.04Hil 634 0.02 Mal 0.23 Lck 0.02 Hbt 564|0.056|25|1.372|85660|0.082|25|1.015|85 930|0.036|25|0.378|85 0.2 Hir 635 0.01 Mal 0.34Lck 0.16 Hr 565|0.089|25|0.666|85 624|0.132|25|0.502|85985|0.045|25|0.201|85 0.08 Hij 636 0.01 Mo 0.76 Lbg 0.039 Hir587|0.088|25|0.626|85 653|0.029|25|0.533|85 747|0.018|25|0.536|85 0.033Hiu 637 0.02 Mak 0.52 Le 0.2 Hfz 704|0.212|25|2.578|85756|0.197|25|2.485|85 638 0.01 Mal 0.18 Lck 0.01 Hbt 403|0.229|25|5|85562|0.055|25|1.843|85 681|0.043|25|0.643|85 0.1 Hir 0.02 Hke 639 0.02Mak 1.01 Lai 0.2 Hfz 668|0.279|25|2.181|85 704|0.39|25|2.543|85756|0.39|25|2.432|85 640 0.01 Mal 0.021 Lck 0.05 Hbj503|0.197|25|3.871|85 535|0.174|25|3.789|85 723|0.049|25|0.677|85 0.053Hir 641 0.01 Mal 0.075 Lck 0.03 Hcp 492|0.464|25|4.127|65761|0.095|25|1.151|85 817|0.054|25|0.995|85 0.05 Hir 642 0.02 Mal 0.16Lck 0.08 Hcp 581|0.157|25|0.526|85 643 0.02 Mal 0.16 Lck 0.02 Hbl503|0.102|25|1.153|85 700|0.063|25|0.512|85 985|0.067|25|0.426|85 0.1Hij 644 0.01 Mh 1.32 Lck 0.04 Hil 554|0.096|25|1.353|65590|0.108|25|1.836|65 637|0.126|25|2.243|65 645 0.02 Mak 0.53 Lad 0.2Hfz 668|0.259|25|2.489|85 704|0.34|25|3.018|85 756|0.321|25|2.885|85 6460.01 Mal 0.036 Lck 0.03 Har 385|0.893|25|5|65 569|0.128|25|3.114|851032|0.055|25|0.606|85 0.1 Hir 0.1 Hke 647 0.01 Mo 1.38 Lck 0.1 Hij572|0.134|25|1.695|85 626|0.19|25|2.573|85 664|0.184|25|2.73|85 0.02 Hil648 0.005 Mal 0.013 Lck 0.05 Har 385|0.25|25|5|85 603|0.064|25|0.9|85668|0.066|25|0.695|85 0.05 Hir 0.02 Hke 649 0.02 Mal 0.069 Lck 0.02 Had496|0.038|25|0.201|85 704|0.105|25|0.875|85 756|0.071|25|0.838|85 0.1Hij 650 0.02 Mal 0.35 Lck 0.04 Hcq 531|0.132|25|0.471|85650|0.188|25|0.449|85 701|0.143|25|0.446|85 0.14 Hij 651 0.01 Mo 0.24Lck 0.047 Hii 542|0.299|25|0.406|85 586|0.149|25|0.364|85632|0.079|25|0.316|85 652 0.02 Mal 0.6 Lck 0.02 Heo535|0.296|25|1.443|85 571|0.358|25|1.643|85 990|0.184|25|0.677|85 0.041Hje 653 0.0202 Mal 0.186 Lck 0.214 Hij 673|0.134|25|1.933|85705|0.169|25|2.54|85 757|0.158|25|2.534|85 654 0.0201 Mal 0.115 Lck0.106 Hij 671|0.08|25|1.195|85 706|0.092|25|1.556|85756|0.078|25|1.535|85 655 0.02 Mal 0.38 Lck 0.08 Hcp645|0.164|25|2.304|85 684|0.172|25|2.236|85 0.08 Hik 656 0.01 Mal 0.295Lcn 0.02 Hv 411|0.091|25|0.172|85 503|0.03|25|0.261|85 657 0.01 Mo 0.59Lck 0.01 Hh 442|2.133|25|2.384|85 638|0.344|25|2.292|85670|0.386|25|2.875|85 0.02 Hfz 658 0.01 Mao 0.063 Lbd 0.01 Hgm491|0.153|25|0.612|85 0.01 Mal 659 0.02 Mal 0.1 Lck 0.15 Heg608|0.107|25|1.057|85 700|0.136|25|1.781|85 751|0.094|25|1.374|85 0.1Hij 660 0.02 Mal 0.098 Lck 0.55 Hl 606|0.052|25|0.676|85656|0.066|25|1.02|85 702|0.069|25|1.065|85 0.103 Hij 661 0.01 Mal 0.16Lbd 0.02 Hv 418|0.14|25|0.498|85 505|0.051|25|1.145|85 662 0.02 Mal 2.26Lbs 0.1 Hab 595|0.148|25|1.746|85 645|0.175|25|1.526|851025|0.097|25|0.479|85 0.2 Hij 663 0.02 Mal 0.29 Lck 0.04 Haj426|0.368|25|2.736|85 626|0.217|25|2.307|85 1012|0.08|25|0.437|85 0.16Hco 0.1 Hij 664 0.02 Mal 0.18 Lck 0.1 Hco 421|0.249|25|5|85683|0.072|25|1.408|85 731|0.061|25|1.504|85 0.061 Hij 665 0.02 Mal 2.84Lbd 0.06 Haj 560|0.043|25|1.066|85 616|0.075|25|1.458|851014|0.047|25|0.297|85 0.06 Hij 666 0.01 Mal 1.26 Lbs 0.02 Hje570|0.135|25|0.928|85 640|0.111|25|0.699|85 908|0.101|25|0.627|85 0.6Hke 667 0.02 Mal 2.39 Lbd 0.06 Haj 557|0.069|25|1.305|85615|0.108|25|1.866|85 1010|0.055|25|0.381|85 0.06 Hij 668 0.02 Mal 0.36Lck 0.04 Hje 589|0.112|25|1.037|85 643|0.124|25|0.98|85954|0.056|25|0.436|85 0.5 Hke 669 0.01 Mo 0.057 Lck 0.49 Hca575|0.282|25|0.898|85 595|0.284|25|0.929|85 747|0.838|25|2.671|85 0.02Hir 670 0.02 Mal 0.052 Lck 0.085 Hct 655|0.175|25|1.455|85702|0.209|25|1.365|85 746|0.177|25|1.144|85 0.06 Hij 671 0.01 Mal 0.27Lbq 0.02 Hv 413|0.14|25|0.635|85 504|0.067|25|1.647|85 672 0.002 Mal0.0024 Lck 0.004 Hdm 391|0.162|25|2.315|85 458|0.042|25|1.139|85521|0.024|25|0.646|85 0.02 Hir 0.2 Hkf 673 0.02 Mak 0.2 Lbg 0.02 Hfz794|0.138|25|1.217|85 0.2 Hir 674 0.02 Mak 0.16 Lcg 0.2 Hfz703|0.172|25|2.084|85 756|0.15|25|2.035|85 675 0.01 Mo 0.2 Lck 0.04 Hrc506|0.491|25|2.868|85 578|0.074|25|0.35|85 676 0.003 Mal 0.065 Lck 0.03Hir 418|0.135|25|3.871|85 505|0.059|25|1.723|85 563|0.061|25|1.696|850.03 Hjr 677 0.01 Mao 0.77 Lbs 0.02 Hgm 493|0.188|25|0.998|85 0.01 Mal678 0.01 Mo 0.47 Lck 0.06 Hgh 536|0.175|25|0.782|85576|0.127|25|1.022|85 612|0.085|25|0.798|85 0.5 Lco 679 0.02 Mal 0.095Lck 0.52 Hej 608|0.102|25|0.962|85 637|0.144|25|1.06|85700|0.15|25|0.706|85 0.04 Hij 680 0.02 Mak 0.32 Lbg 0.02 Hfw531|0.072|25|2.947|85 760|0.128|25|0.69|85 0.2 Hir 681 0.02 Mal 0.14 Lck0.06 Hns 631|0.158|25|1.704|85 694|0.14|25|1.205|851194|0.087|25|0.417|85 0.1 Hij 682 0.02 Mal 0.095 Lck 0.02 Hnm450|0.229|25|1.754|85 544|0.083|25|0.368|85 781|0.091|25|0.466|85 0.06Hij 683 0.01 Mal 1.13 Lcz 0.02 Hv 419|0.095|25|0.327|85503|0.059|25|0.762|85 684 0.02 Mal 0.11 Lck 0.02 Hnm414|0.57|25|1.294|85 662|0.323|25|0.454|85 0.06 Hja 685 0.02 Mal 0.6 Ldc0.02 Hnt 536|0.135|25|0.429|85 0.024 Hje 686 0.01 Mo 0.74 Lck 0.01 Hnm538|0.342|25|0.545|85 604|0.318|25|0.979|85 625|0.282|25|0.912|85 0.011Hij 687 0.01 Mo 1.36 Lck 0.1 Hfz 568|24|0.509|85 647|24|1.599|85665|24|1.654|85 0.01 Hgm 688 0.01 Mo 1.8 Lck 0.01 Han572|0.631|25|1.491|85 658|0.837|25|2.36|85 683|0.917|25|2.589|85 0.03Hje 689 0.01 Mal 0.48 Lck 0.05 Hrc 506|0.025|25|0.345|85 0.03 Hij 6900.02 Mal 0.31 Lck 0.1 Hdv 595|0.126|25|0.95|85 655|0.145|25|0.787|851039|0.084|25|0.287|85 0.061 Hij 691 0.02 Mal 0.38 Lck 0.04 Hgz485|0.04|25|0.536|85 653|0.131|25|0.807|85 705|0.081|25|0.774|85 0.2 Hje692 0.02 Mal 0.085 Lck 0.05 Hdf 608|0.241|25|1.376|85642|0.23|25|1.462|85 697|0.175|25|1.244|85 0.08 Hij 693 0.04 Mal 0.24Lck 0.02 Hhb 433|0.877|25|2.641|85 706|0.32|25|1.681|85755|0.269|25|1.59|85 0.2 Hij 694 0.04 Mal 2.05 Lbs 0.04 Hbt548|0.087|25|2.455|85 611|0.155|25|2.471|85 970|0.107|25|1.142|85 0.12Hij 695 0.02 Mal 0.74 Lck 0.0102 Hm 555|0.11|25|1.417|85595|0.107|25|1.064|85 1036|0.08|25|0.43|85 0.3 Hij 696 0.04 Mal 0.56 Lck0.026 Hbt 426|0.548|25|1.684|85 545|0.16|25|0.927|85630|0.207|25|1.048|85 0.015 Hhb 0.3 Hij 697 0.005 Ma 0.045 Lck 0.025 Hir390|0.243|25|5|85 510|0.037|25|1.862|85 670|0.054|25|0.674|85 0.015 Hke698 0.04 Mal 0.31 Lck 0.025 Hgm 430|0.612|25|1.849|85521|0.144|25|0.739|85 700|0.237|25|0.627|85 0.015 Hhb 0.2 Hij 699 0.01Mal 0.095 Lbs 0.058 Hai 556|0.045|25|0.848|85 619|0.082|25|1.268|85987|0.045|25|0.267|85 0.04 Hij 700 0.01 Mal 0.92 Lbs 0.127 Hai556|0.043|25|1.085|85 602|0.076|25|1.238|85 986|0.049|25|0.351|85 0.04Hij 701 0.005 Mf 0.77 Lbs 0.005 Haj 412|0.232|25|4.519|85560|0.059|25|3.114|85 735|0.033|25|0.979|85 0.05 Hir 0.016 Hke 702 0.02Mal 0.14 Lck 0.2 Hfz 498|0.067|25|1.162|85 866|0.074|25|0.366|85994|0.101|25|0.437|85 0.02 Hbf 703 0.02 Mal 0.35 Lck 0.04 Hdp630|0.244|25|2.617|85 1134|0.075|25|0.581|85 0.2 Hfz 704 0.02 Mal 0.16Lck 0.037 Hff 661|0.104|25|1.956|85 694|0.118|25|2.037|85734|0.105|25|1.924|85 0.12 Hij 705 0.01 Mo 0.35 Hgi535|0.457|25|1.126|85 571|0.56|25|1.776|85 600|0.463|25|1.681|85 0.01Hjg 706 0.01 Mal 0.25 Lck 0.04 Hfz 377|0.3|25|3.008|65679|0.048|25|0.649|85 1046|0.035|25|0.294|85 0.1 Hir 0.02 Hke 707 0.01Mo 1.21 Lck 0.2 Hfz 590|0.104|25|1.002|85 663|0.131|25|3.084|85698|0.042|25|2.706|85 0.04 Hgp 708 0.04 Mal 0.37 Lck 0.021 Hbs487|0.042|25|0.927|85 632|0.263|25|1.018|85 945|0.098|25|0.528|85 0.05Hhh 0.13 Hje 709 0.02 Mak 1.3 Lcs 0.2 Hfz 706|0.535|25|3.47|65756|0.507|25|3.232|65 710 0.02 Mak 0.75 Lag 0.2 Hfz 667|0.08|25|1.514|85705|0.104|25|1.769|85 756|0.089|25|1.659|85 711 0.005 Mal 0.015 Lck0.005 Hci 395|0.073|25|2.736|85 513|0.02|25|1.833|85819|0.006|25|0.237|85 0.05 Hir 712 0.01 Mal 0.17 Lck 0.005 Hbt652|0.094|25|0.841|85 1025|0.051|25|0.376|85 0.02 Hfz 0.1 Hir 713 0.02Mak 0.056 Hjf 555|0.108|25|0.418|85 625|0.067|25|0.289|85 0.051 Hjg 7140.02 Mal 0.25 Lck 0.2 Hfz 514|0.051|25|0.225|85 700|0.098|25|0.306|85756|0.059|25|0.259|85 0.02 Hez 715 0.02 Mal 0.15 Lck 0.02 Hcw665|0.099|25|0.302|85 702|0.108|25|0.392|85 756|0.084|25|0.373|85 0.2Hfz 716 0.02 Mak 1.51 Lab 0.2 Hfz 658|0.308|25|1.376|85705|0.394|25|1.314|85 755|0.391|25|1.221|85 717 0.02 Mak 0.18 Lch 0.2Hfz 669|0.167|25|1.857|85 704|0.221|25|2.38|85 757|0.201|25|2.319|85 7180.01 Mo 0.86 Lck 0.01 Hje 597|0.369|25|1.154|85 647|0.598|25|1.756|85667|0.718|25|1.948|85 0.6 Hkf 719 0.003 Mal 0.024 Lck 0.03 Hir395|0.036|25|0.642|85 500|0.01|25|0.307|85 735|0.012|25|0.081|85 0.006Hjy 720 0.01 Mo 0.67 Lck 1 Hhh 620|0.221|25|2.573|85648|0.261|25|3.539|85 687|0.179|25|2.798|85 0.049 Hir 721 0.01 Mo 0.07Lbg 0.15 Hgi 532|0.277|25|0.96|85 575|0.221|25|1.391|85 722 0.02 Mal0.26 Lck 0.01 Hbu 521|0.028|25|0.628|85 632|0.319|25|1.6|85981|0.065|25|0.304|85 0.01 Hdp 0.2 Hfz 723 0.01 Mo 0.55 Lck 0.12 Hwq550|0.076|25|0.359|85 583|0.097|25|0.478|85 636|0.126|25|0.612|85 7240.002 Mal 0.0054 Lck 0.02 Hir 380|0.138|25|1.248|85500|0.012|25|0.202|85 680|0.034|25|0.162|85 0.4 Hkf 725 0.02 Mal 0.44Lck 0.04 Hdp 565|0.087|25|1.517|85 607|0.155|25|1.771|851108|0.077|25|0.438|85 0.1 Hje 726 0.005 Maf 0.11 Lck 0.2 Hke430|0.24|25|2.002|85 635|0.032|25|0.28|85 1025|0.02|25|0.136|85 727 0.02Mak 0.69 Lbg 0.1 Hcb 655|0.241|25|1.589|85 688|0.258|25|1.464|85 0.1 Hfz728 0.02 Mal 0.47 Lck 0.04 Hdm 606|0.123|25|1.596|85652|0.171|25|1.207|85 1111|0.068|25|0.396|85 0.1 Hen 729 0.02 Mal 0.4Lck 0.02 Hbt 620|0.377|25|1.306|85 666|0.531|25|1.33|851009|0.138|25|0.323|85 0.2 Hja 730 0.005 Mal 0.036 Lck 0.015 Hhc528|0.119|25|1.323|85 708|0.029|25|0.287|85 0.005 Hke 731 0.01 Mal 0.18Lck 0.06 Hcn 492|0.201|25|5|85 792|0.023|25|0.809|85 0.1 Hir 732 0.02Mak 1.1 Lbg 0.04 Hfw 620|0.208|25|1.589|85 0.1 Hje 733 0.04 Mak 0.13 Lck0.2 Hfz 505|0.12|25|1.662|85 702|0.4|25|1.943|85 755|0.265|25|1.829|850.02 Hbs 734 0.02 Mal 0.24 Lck 0.02 Har 553|0.064|25|0.85|85625|0.152|25|1.569|85 1140|0.079|25|0.36|85 0.06 Hij 0.04 Hke 735 0.01Mo 2.3 Lck 0.1 Hff 605|0.2|25|1.278|85 686|0.454|25|2.739|85 0.1 Hfz 7360.01 Mo 0.06 Hga 600|0.214|25|1.988|85 635|0.179|25|2.254|85665|0.148|25|2.395|85 0.9 Hcv 737 0.01 Mo 1.63 Lck 0.02 Hij624|0.097|25|0.902|85 667|0.114|25|1.25|85 694|0.057|25|0.91|85 0.2 Hna738 0.005 Mal 0.03 Lck 0.05 Hei 530|0.11|25|2.481|85715|0.025|25|0.527|85 0.05 Hir 739 0.01 Mo 0.1 Hfz 532|0.213|25|0.403|85576|0.125|25|0.454|85 0.21 Hin 740 0.02 Mak 0.93 Lbg 0.02 Hfw623|0.211|25|1.511|85 654|0.225|25|1.451|85 697|0.189|25|1.129|85 0.1Hje 741 0.01 Mh 0.93 Lbg 0.03 Hea 590|0.277|25|1.057|85660|0.365|25|2.274|85 742 0.02 Mal 0.25 Lck 0.01 Hea481|0.102|25|0.755|85 652|0.118|25|0.97|85 704|0.138|25|1|85 0.1 Hje 7430.02 Mak 0.76 Lal 0.2 Hfz 664|0.125|25|1.255|85 703|0.125|25|1.441|85755|0.105|25|1.335|85 744 0.007 Mq 0.022 Lar 0.12 Hfz498|0.038|25|0.486|85 760|2.531|25|2.154|85 745 0.02 Mak 2.16 Lbg 0.04Hfo 626|0.164|25|0.905|85 680|0.141|25|0.78|85 1020|0.091|25|0.408|850.16 Hfz 746 0.01 Mo 0.67 Lck 0.1 Hfz 641|0.118|25|2.009|85700|0.143|25|2.948|85 724|0.106|25|2.205|85 0.03 Hgh 747 0.01 Mo 0.2 Lck0.1 Hfi 515|0.189|25|0.494|85 572|0.137|25|0.512|85 599|0.106|25|0.46|85748 0.02 Mal 0.12 Lck 0.04 Hqn 503|0.135|25|0.901|85667|0.084|25|0.366|85 981|0.087|25|0.366|85 0.1 Hij 749 0.02 Mal 0.61Lbs 0.02 Htq 558|0.09|25|0.786|85 603|0.111|25|0.876|851002|0.096|25|0.375|85 0.1 Hij 750 0.02 Mal 0.79 Lbs 0.02 Hof551|0.1|25|0.786|85 611|0.191|25|0.903|85 992|0.114|25|0.354|85 0.1 Hij751 0.02 Mal 0.55 Lbs 0.02 Htp 417|0.389|25|1.912|85503|0.209|25|2.017|85 948|0.133|25|0.791|85 0.1 Hij 752 0.01 Mal 0.17Lbs 0.01 Htm 533|0.088|25|0.538|85 706|0.055|25|0.274|85950|0.034|25|0.17|85 0.03 Hij 753 0.02 Mal 0.86 Lck 0.02 Hto429|0.135|25|0.957|85 512|0.087|25|1.063|85 858|0.046|25|0.396|85 0.1Hij 754 0.02 Mal 0.94 Lbs 0.012 Hbs 414|0.245|25|1.234|85503|0.099|25|1.291|85 704|0.097|25|0.616|85 0.2 Hij 755 0.02 Mal 0.5 Lbs0.02 Htk 564|0.158|25|0.902|85 597|0.215|25|0.984|851010|0.102|25|0.359|85 0.061 Hij 756 0.02 Mal 0.53 Lbs 0.02 Hrl651|0.27|25|1.406|85 685|0.291|25|1.427|85 1196|0.14|25|0.343|85 0.06Hij 757 0.04 Mal 0.72 Lbs 0.027 Hgz 502|0.134|25|1.576|85663|0.262|25|1.566|85 967|0.206|25|0.725|85 0.2 Hij 0.011 Hja 758 0.02Mal 1.05 Lbs 0.1 Hos 621|0.06|25|1.543|85 651|0.084|25|1.7|85691|0.091|25|1.529|85 0.1 Hij 759 0.02 Mal 0.85 Lbs 0.06 Hrk616|0.163|25|1.338|85 642|0.191|25|1.436|85 1206|0.132|25|0.401|85 7600.02 Mal 0.3 Lbs 0.02 Hpg 513|0.132|25|0.584|85 670|0.189|25|1.473|85755|0.208|25|1.724|85 0.1 Hij 761 0.02 Mat 654|0.168|25|0.568|85704|0.182|25|0.49|85 751|0.164|25|0.454|85 762 0.005 Mal 0.026 Lck 0.005Hur 499|0.068|25|0.99|85 813|0.057|25|0.308|85 897|0.061|25|0.296|850.026 Hij 763 0.02 Mal 1.49 Lbs 0.02 Huj 514|0.053|25|1.301|85590|0.038|25|0.628|85 652|0.077|25|0.607|85 0.1 Hij 764 0.02 Mal 1.21Lbs 0.02 Hui 413|0.349|25|2.608|85 523|0.084|25|1.259|85648|0.141|25|1.179|85 0.1 Hij 765 0.02 Mal 0.74 Lbs 0.02 Htd522|0.124|25|1.765|85 854|0.077|25|0.643|85 957|0.115|25|0.759|85 0.1Hij 766 0.02 Mal 0.089 Lbs 0.04 Hst 419|0.106|25|1.436|85520|0.081|25|0.769|85 620|0.093|25|0.943|85 0.2 Hij 767 0.02 Mal 0.59Lbs 0.005 Hou 503|0.15|25|1.497|85 655|0.166|25|0.925|85855|0.081|25|0.542|85 0.008 Hbs 0.1 Hij 768 0.02 Mal 0.09 Lbd 0.02 Hgm506|0.086|25|0.538|85 0.02 Him 769 0.005 Mf 0.11 Lck 0.04 Hrm417|0.078|25|0.896|85 562|0.033|25|0.422|85 745|0.01|25|0.127|85 7700.02 Mal 0.83 Lbs 0.02 Huj 514|0.144|25|1.786|85 653|0.118|25|0.701|851011|0.095|25|0.604|85 0.05 Hij 771 0.02 Mal 0.35 Lbs 0.04 Hha530|0.079|25|1.163|85 649|0.072|25|0.401|85 960|0.059|25|0.557|85 0.04Hij 772 0.02 Mal 1.13 Lbs 0.036 Hwc 553|0.099|25|1.67|85605|0.156|25|2.121|85 972|0.072|25|0.522|85 0.1 Hij 773 0.003 Mbo 0.022Lck 0.003 Hwc 388|0.152|25|2.507|85 509|0.051|25|1.105|85700|0.022|25|0.264|85 0.027 Hir 0.001 Hke 774 0.03 Mal 1.02 Lbs 0.015Hwa 611|0.081|25|2.043|85 652|0.125|25|2.467|85 751|0.091|25|1.646|850.2 Hij 775 0.005 Mbn 0.032 Lck 418|0.153|25|2.358|85563|0.061|25|1.04|85 745|0.02|25|0.261|85 776 0.02 Mal 1.92 Lbs 0.02 Hvw553|0.142|25|2.363|85 591|0.131|25|1.779|85 1029|0.095|25|0.689|85 0.1Hij 777 0.02 Mal 1.23 Lbs 0.01 Hvn 418|0.249|25|1.705|85506|0.086|25|1.26|85 646|0.074|25|0.475|85 0.1 Hij 778 0.02 Mal 1.38 Lbs0.02 Hvo 518|0.058|25|1.609|85 645|0.072|25|0.489|85970|0.05|25|0.628|85 0.1 Hij 779 0.02 Mal 1.41 Lbs 0.02 Hvn506|0.074|25|1.867|85 633|0.074|25|0.478|85 950|0.051|25|0.666|85 0.1Hij 780 0.02 Mal 1 Lbs 0.02 Hou 436|0.329|25|1.118|85553|0.079|25|0.629|85 594|0.147|25|0.612|85 0.1 Hij 781 0.02 Mal 2.6 Lbd0.2 Hij 658|0.085|25|2.734|85 703|0.104|25|2.231|85748|0.098|25|1.587|85 782 0.02 Mal 0.47 Lbs 0.02 Hry515|0.118|25|1.294|85 559|0.117|25|0.876|85 986|0.124|25|0.561|85 0.1Hij 783 0.02 Mal 1.52 Lbs 0.02 Hss 415|0.224|25|2.428|85507|0.074|25|1.894|85 953|0.047|25|0.676|85 0.1 Hij 784 0.02 Mal 1.15Lbs 0.008 Haz 527|0.074|25|0.966|85 654|0.07|25|0.694|85754|0.063|25|0.62|85 0.15 Hij 785 0.02 Mal 0.047 Lbs 0.04 Hsz502|0.186|25|1.277|85 701|0.249|25|1.009|85 957|0.147|25|0.538|85 0.2Hij 786 0.02 Mal 0.05 Lbs 0.04 Hst 520|0.084|25|0.787|85603|0.104|25|0.946|85 974|0.097|25|0.482|85 0.1 Hij 787 0.02 Mal 0.34Lbs 0.03 Hst 520|0.053|25|0.491|85 604|0.098|25|0.576|85976|0.1|25|0.332|85 0.1 Hij 788 0.02 Mal 0.81 Lbs 0.007 Hoz497|0.111|25|1.113|85 558|0.086|25|1.086|85 642|0.125|25|1.043|85 0.008Htq 0.15 Hij 789 0.02 Mal 1.34 Lbs 0.02 Hsc 528|0.129|25|1.288|85649|0.071|25|0.434|85 990|0.074|25|0.492|85 0.1 Hij 790 0.02 Mal 0.93Lbs 0.02 Hrz 514|0.087|25|1.079|85 565|0.077|25|0.614|85987|0.107|25|0.443|85 0.1 Hij 791 0.01 Mal 0.088 Lcd 0.02 Hv500|0.093|25|0.821|85 792 0.02 Mal 0.14 Lbs 0.02 Hvm507|0.105|25|1.364|85 706|0.251|25|0.868|85 970|0.111|25|0.586|85 0.06Hij 793 0.01 Mal 0.72 Lp 0.02 Hv 420|0.153|25|0.843|85502|0.272|25|2.369|85 794 0.02 Mal 1.85 Lbs 0.02 Hgk538|0.098|25|1.122|85 860|0.044|25|0.376|85 967|0.056|25|0.376|85 0.1Hij 795 0.01 Mao 0.14 Ldg 0.02 Hgm 492|0.173|25|0.885|85 0.01 Mal 7960.01 Mao 0.069 Ldh 0.02 Hgm 492|0.172|25|0.845|85 0.01 Mal 797 0.02 Mal0.083 Lck 0.1 Hpj 628|0.225|25|2.311|85 691|0.205|25|1.765|851145|0.099|25|0.51|85 0.1 Hij 798 0.02 Mal 0.32 Lck 0.063 Hij615|0.24|25|2.339|85 668|0.306|25|1.971|85 1049|0.165|25|0.518|85 0.1Hja 799 0.02 Mal 0.23 Lck 0.1 Hij 658|0.133|25|1.308|85704|0.102|25|1.039|85 1200|0.118|25|0.24|85 0.02 Hja 800 0.02 Mal 0.12Lck 0.1 Hnw 690|0.068|25|1.214|85 731|0.061|25|1.261|851242|0.054|25|0.24|85 0.06 Hij 801 0.02 Mal 0.14 Lck 0.1 Hpo646|0.122|25|0.962|85 693|0.103|25|0.848|85 1200|0.075|25|0.217|85 0.06Hij 802 0.005 Me 1.31 Lbs 0.15 Hke 382|0.142|25|1.505|85432|0.125|25|1.383|85 627|0.016|25|0.124|85 803 0.01 Mo 0.41 Lck 0.02Hnu 533|0.231|25|0.427|85 565|0.247|25|0.505|85 603|0.221|25|0.466|85804 0.01 Mo 0.055 Lbd 0.02 Hv 492|0.195|25|0.433|85 805 0.02 Mal 0.15Lck 0.02 Hnm 450|0.129|25|1.426|85 777|0.069|25|0.387|85 0.06 Hij 8060.02 Mal 0.39 Lck 0.2 Hij 651|0.152|25|2.039|85 699|0.125|25|1.58|851200|0.104|25|0.474|85 0.2 Hna 807 0.02 Mal 0.097 Lck 0.021 Hnd663|0.139|25|1.578|85 701|0.135|25|1.662|85 752|0.09|25|1.276|85 0.1 Hij808 0.005 Mal 0.1 Lck 0.024 Hnh 412|0.094|25|2.354|85555|0.031|25|0.95|85 738|0.013|25|0.234|85 0.06 Hir 809 0.02 Mal 0.077Lck 0.1 Hnf 428|0.682|25|3.517|85 704|0.152|25|2.202|85753|0.13|25|2.023|85 0.1 Hij 810 0.01 Mal 0.36 Lck 0.02 Hij405|2.17|25|5|85 570|0.115|25|0.373|85 0.1 Hng 811 0.01 Mal 1.92 Lbs 0.3Hnh 411|1.09|25|5|85 581|0.123|25|0.582|85 900|0.04|25|0.151|85 0.02 Hij812 0.01 Mao 0.084 Lbd 0.02 Hgm 493|0.195|25|0.999|85 0.01 Mal 813 0.01Mo 0.54 Lck 0.042 Hnh 636|0.222|25|1.466|85 704|0.214|25|1.851|85 0.02Hij 814 0.01 Mo 0.58 Lck 0.021 Hij 641|0.125|25|1.319|85678|0.133|25|1.659|85 703|0.149|25|1.807|85 0.043 Hng 815 0.02 Mal 1.5Lbs 0.08 Hab 580|0.252|25|2.342|85 648|0.262|25|1.703|851010|0.131|25|0.662|85 0.02 Haj 0.06 Hij 816 0.02 Mal 0.16 Lck 0.041 Hij620|0.257|25|1.501|85 649|0.274|25|1.465|85 1110|0.108|25|0.342|85 0.2Hna 817 0.02 Mal 1.52 Lbs 0.02 Hss 416|0.276|25|2.436|85507|0.089|25|1.884|85 860|0.04|25|0.604|85 0.1 Hij 818 0.02 Mal 0.214Lck 0.025 Hri 434|0.369|25|1.639|85 717|0.112|25|0.501|85 0.061 Hij 8190.02 Mal 0.65 Lbt 0.2 Hrg 560|0.411|25|1.207|85 723|0.421|25|1.052|85820 0.02 Mas 0.27 Lbt 560|0.394|25|1.207|85 722|0.317|25|0.991|85 8210.02 Mal 0.11 Lbt 0.2 Har 602|0.502|25|2.307|85 992|0.218|25|0.614|850.1 Hij 822 0.02 Mal 0.15 Lbt 0.15 Hik 484|0.028|25|0.246|85656|0.243|25|2.324|85 704|0.183|25|2.357|85 823 0.02 Mal 0.1 Lbt 0.15Hik 654|0.381|25|2.649|85 704|0.331|25|2.703|85 824 0.005 Mo 0.094 Lck0.025 Hgz 503|0.094|25|1.504|85 642|1.129|25|1.579|85964|0.118|25|0.597|85 0.02 Mal 0.2 Hij 825 0.02 Mal 0.07 Lck 0.1 Hnv662|0.072|25|0.889|85 704|0.076|25|0.991|85 754|0.061|25|0.945|85 0.061Hij 826 0.02 Mal 0.12 Lck 0.1 Hnw 686|0.087|25|1.159|85727|0.068|25|1.196|85 1235|0.054|25|0.232|85 0.06 Hij 827 0.04 Mal 0.25Lck 0.016 Hbt 450|0.121|25|1.023|85 511|0.065|25|0.971|85609|0.258|25|1.042|85 0.015 Hnm 0.01 Hgz 828 0.01 Mo 0.8 Lck 0.1 Hfz617|0.096|25|1.228|85 665|0.066|25|1.251|85 697|0.046|25|1.165|85 0.05Hgh 829 0.04 Mal 0.27 Lck 0.016 Hbt 451|0.128|25|0.844|85547|0.125|25|1.115|85 600|0.208|25|1.085|85 0.015 Hbl 0.015 Hnm 830 0.04Mal 0.275 Lck 0.031 Hbt 449|0.13|25|1.175|85 545|0.131|25|1.175|85603|0.236|25|1.151|85 0.023 Hnm 0.12 Hij 831 0.04 Mal 0.13 Lck 0.08 Ho448|0.31|25|1.9|85 708|0.194|25|1.042|85 757|0.167|25|1.131|85 0.02 Hnm0.12 Hij 832 0.02 Mal 0.13 Lck 0.06 Hnu 606|0.221|25|1.056|85645|0.221|25|1.068|85 694|0.125|25|0.912|85 0.06 Hij 833 0.02 Mal 0.1Lck 0.02 Hnu 598|0.128|25|0.753|85 653|0.131|25|0.941|85700|0.102|25|0.898|85 0.061 Hij 834 0.04 Mal 0.14 Lck 0.02 Hbl454|0.273|25|1.86|85 498|0.206|25|2.061|85 758|0.154|25|0.851|85 0.02Hnm 0.12 Hij 835 0.02 Mal 0.18 Lck 0.1 Hog 688|0.071|25|1.163|85731|0.06|25|1.231|85 1210|0.067|25|0.238|85 0.062 Hij 836 0.04 Mal 0.14Lck 0.02 Hbl 455|0.353|25|1.666|85 496|0.255|25|1.882|85753|0.189|25|0.824|85 0.02 Hnm 0.11 Hij 837 0.0105 Mao 0.023 Ldf 0.021Hgm 492|0.326|25|1.112|85 0.0105 Mal 838 0.02 Mal 0.145 Lck 0.1 Hnw677|0.155|25|1.338|85 715|0.115|25|1.359|85 1232|0.069|25|0.257|85 0.06Hij 839 0.01 Mal 0.13 Lck 0.03 Har 376|0.534|25|1.756|85632|0.054|25|0.706|85 793|0.022|25|0.089|85 0.05 Hff 0.1 Hir 840 0.02Mal 0.21 Lck 0.01 Hdp 518|0.16|25|0.987|85 611|0.281|25|1.2|85969|0.118|25|0.443|85 0.2 Hfz 0.01 Haz 841 0.02 Mak 0.16 Lck 0.02 Hdo635|0.175|25|1.686|85 0.1 Hfz 842 0.02 Mal 0.39 Lck 0.1 Hcr582|0.247|25|1.578|85 645|0.26|25|1.186|85 1015|0.108|25|0.438|85 0.06Hij 843 0.02 Mal 0.08 Lck 0.06 Hac 610|0.083|25|0.465|85660|0.095|25|0.543|85 700|0.081|25|0.511|85 0.06 Hij 844 0.02 Mal 0.29Lck 0.01 Hdp 503|0.027|25|0.589|85 633|0.165|25|1.083|85973|0.079|25|0.288|85 0.2 Hfz 0.015 Hgz 845 0.01 Mo 1.7 Lck 0.02 Hfz595|0.215|25|1.623|85 630|0.307|25|2.391|85 649|0.347|25|2.637|85 0.1Hhh 846 0.01 Mo 0.37 Lck 0.02 Hfz 642|0.175|25|1.159|85699|0.272|25|1.848|85 750|0.14|25|0.839|85 0.1 Hka 847 0.02 Mal 0.067Lck 0.02 Hv 395|0.129|25|0.377|85 500|0.11|25|1.132|85 848 0.01 Mo 2.3Lck 0.02 Hea 565|0.159|25|0.793|85 656|0.159|25|1.785|85 0.1 Hje 8490.01 Mh 0.019 Lu 0.03 Hea 508|0.618|25|0.507|85 665|0.149|25|1.125|85723|0.122|25|1.005|85 0.15 Hfz 850 0.02 Mal 0.21 Lck 0.02 Hra502|0.449|25|2.075|85 639|0.228|25|0.742|85 988|0.196|25|0.85|85 0.105Hik 851 0.02 Mak 0.4 Lbg 0.08 Hfz 715|0.2|25|1.917|85761|0.194|25|2.003|85 0.2 Hir 852 0.02 Mal 0.59 Lck 0.1 Har395|0.387|25|0.142|85 525|0.055|25|1.225|85 570|0.094|25|1.492|85 0.1Hik 853 0.003 Mal 0.17 Lck 0.03 Hir 421|0.083|25|1.533|85504|0.069|25|0.94|85 555|0.044|25|0.685|85 0.03 Hjs 854 0.0204 Mal 0.917Lck 0.993 Hij 705|0.115|25|2.152|85 757|0.102|25|2.143|85 855 0.01 Mal0.023 Lck 0.032 Har 389|0.316|25|5|85 513|0.016|25|1.302|85658|0.101|25|0.701|85 0.1 Hfe 0.1 Hir 856 0.02 Mal 0.19 Lck 0.01 Hbu518|0.056|25|0.955|85 695|0.192|25|1.184|85 753|0.138|25|1.157|85 0.2Hfz 0.01 Hje 857 0.01 Mo 1.54 Lck 0.1 Hfz 634|0.252|25|2.97|85688|0.186|25|2.604|85 720|0.23|25|3.022|85 0.1 Hke 858 0.02 Mak 2.2 Lbg0.02 Hdy 503|0.994|25|2.808|85 885|0.289|25|0.712|85990|0.466|25|1.151|85 0.16 Hfz 859 0.02 Mak 0.48 Lh 0.2 Hfz670|0.384|25|2.653|85 705|0.531|25|3.312|85 757|0.512|25|3.132|85 8600.005 Mo 0.14 Lck 0.2 Hfz 503|0.096|25|1.678|85 642|1.279|25|1.648|85964|0.124|25|0.67|85 0.02 Mal 0.025 Hgz 861 0.008 Mi 0.026 Lu 0.077 Hga498|0.408|25|0.274|85 632|0.241|25|1.085|85 695|0.368|25|1.892|85 8620.01 Mo 1 Lbg 0.08 Hjx 552|0.246|25|0.691|85 605|0.191|25|0.905|85634|0.184|25|0.942|85 863 0.01 Mal 0.32 Lck 0.1 Hir 415|0.23|25|3.61|85595|0.062|25|0.738|85 647|0.077|25|0.85|85 0.02 Hje 0.08 Hke 864 0.02Mal 0.28 Lck 0.04 Hfv 632|0.311|25|3.039|85 1141|0.097|25|0.662|85 0.2Hfz 865 0.002 Mal 0.0045 Lck 0.02 Hir 384|0.135|25|1.902|85504|0.014|25|0.542|85 705|0.024|25|0.218|85 0.2 Hkf 866 0.02 Mak 2.8 Lbg0.047 Hfo 382|1.625|25|5|85 580|0.054|25|0.403|85 648|0.07|25|0.324|850.087 Hje 867 0.003 Mal 0.094 Lck 0.0008 Hij 417|0.066|25|1.958|85561|0.023|25|0.781|85 742|0.002|25|0.205|85 0.03 Hir 0.03 Hke 868 0.01Mal 0.023 Lck 0.032 Har 388|0.327|25|5|85 509|0.013|25|0.968|85602|0.062|25|0.758|85 0.1 Hfe 0.05 Hir 869 0.003 Mo 0.17 Lck 0.01 Hea506|0.308|25|1.85|85 724|3.539|25|2.804|85 1004|0.289|25|0.813|85 0.02Mal 0.2 Hfz 0.01 Hgm 870 0.02 Mak 0.62 Lt 0.2 Hfz 668|0.1|25|2.142|85704|0.126|25|2.544|85 756|0.115|25|2.4|85 871 0.01 Mo 0.73 Lbg 0.033 Hiu535|0.163|25|0.385|85 872 0.01 Mo 0.83 Lck 0.1 Hfz 640|0.282|25|2.202|85666|0.452|25|3.357|85 699|0.665|25|5|85 0.02 Hgw 873 0.0048 Mq 0.0137 Lu0.21 Hfz 506|0.139|25|1.122|85 742|1.473|25|1.069|85 874 0.02 Mal 0.57Lck 0.02 Hg 525|0.122|25|1.241|85 640|0.498|25|0.555|851011|0.1|25|0.503|85 0.06 Hij 875 0.02 Mak 0.34 Ld 0.2 Hfz704|0.825|25|3.47|85 755|0.823|25|3.479|85 876 0.02 Mal 0.18 Lck 0.1 Hag630|0.2|25|1.451|85 692|0.152|25|1.022|85 0.06 Hij 877 0.02 Mal 1.49 Lck0.02 Hgr 497|0.273|25|1.731|85 988|0.159|25|0.775|851206|0.145|25|0.336|85 0.1 Hje 878 0.02 Mak 0.27 Lbg 0.08 Hfz710|0.284|25|2|85 755|0.28|25|1.995|85 0.1 Hir 879 0.02 Mal 0.11 Lck0.02 Hra 519|0.349|25|2.904|85 640|0.195|25|0.614|85996|0.157|25|1.079|85 0.06 Hij 880 0.02 Mal 0.31 Lck 0.004 Hbt531|0.064|25|0.588|85 655|0.144|25|0.487|85 757|0.063|25|0.316|85 0.2Hfz 0.006 Hbb 881 0.01 Mo 3.88 Lbs 0.1 Hfz 618|0.083|25|1.434|85672|0.148|25|2.424|85 700|0.192|25|3.402|85 882 0.01 Mo 1.88 Lck 0.02Hfv 623|0.24|25|2.285|85 652|0.327|25|3.123|85 682|0.358|25|5|85 0.1 Hfz883 0.02 Mak 0.4 Lbg 0.04 Hfw 533|0.067|25|2.734|85 740|0.15|25|0.735|850.2 Hir 884 0.01 Mo 0.28 Lck 0.01 Hgz 538|0.143|25|0.614|85 0.1 Hiu 8850.02 Mal 0.22 Lck 0.02 Hdc 480|0.077|25|0.274|85 702|0.109|25|0.495|85755|0.065|25|0.446|85 0.2 Hfz 886 0.01 Mal 0.1 Lck 0.04 Haw356|0.697|25|3.443|85 660|0.051|25|0.33|85 700|0.04|25|0.31|85 0.04 Hij887 0.01 Mo 0.16 Lck 0.35 Hgi 563|0.07|25|0.783|85 650|0.086|25|1.39|85777|0.097|25|1.582|85 0.15 Hir 888 0.02 Mal 0.26 Lck 0.02 Hfv635|0.309|25|2.706|85 1141|0.105|25|0.594|85 0.2 Hfz 889 0.02 Mak 0.73Laf 0.2 Hfz 670|0.195|25|2.285|85 704|0.237|25|2.785|85756|0.215|25|2.661|85 890 0.01 Mal 0.067 Lck 0.04 Hdp 520|0.032|25|5|85680|0.08|25|1.195|85 0.1 Hir 891 0.02 Mal 0.33 Lbs 0.04 Hbu498|0.111|25|0.558|85 854|0.085|25|0.2|85 959|0.13|25|0.301|85 0.1 Hes892 0.02 Mak 1.6 Lbg 0.16 Hfz 636|0.134|25|1.739|85682|0.144|25|1.623|85 1028|0.089|25|0.806|85 0.17 Hke 893 0.02 Mal 0.12Lck 0.2 Hac 575|0.286|25|0.963|85 665|0.26|25|0.853|851022|0.136|25|0.339|85 0.04 Hij 894 0.01 Mo 0.71 Lck 0.02 Hfz634|0.492|25|2.312|85 688|0.348|25|1.763|85 721|0.447|25|2.111|85 0.2Hke 895 0.001 Mo 0.016 Lck 0.1 Hir 510|0.033|25|1.379|85755|0.899|25|0.988|85 782|1.297|25|1.273|85 0.002 Mal 896 0.02 Mak 0.057Lf 0.2 Hfz 352|0.155|25|5|85 702|0.058|25|0.53|85 756|0.025|25|0.502|85897 0.002 Mak 0.66 Hir 368|1.694|25|4.519|85 496|0.105|25|1.134|85725|0.068|25|0.358|85 0.07 Hjx 898 0.02 Mak 0.7 Lax 0.2 Hfz669|0.282|25|2.018|85 705|0.401|25|2.409|85 756|0.397|25|2.278|85 8990.02 Mak 0.83 Lbg 0.05 Hfz 636|0.196|25|1.461|85 682|0.203|25|1.36|851026|0.114|25|0.695|85 0.17 Hke 900 0.02 Mal 0.1 Lck 0.02 Hbc508|0.051|25|0.139|85 704|0.092|25|0.793|85 756|0.064|25|0.754|85 0.1Hij 901 0.01 Mi 0.029 Lu 0.2 Hga 502|0.478|25|0.294|85632|0.388|25|1.602|85 695|0.634|25|2.849|85 902 0.014 Ek 0.08 Hif539|0.33|25|0.571|85 592|0.327|25|0.757|85 635|0.278|25|0.691|85 0.01 Mo903 0.02 Mal 0.28 Lck 0.06 Hbt 548|0.097|25|1.134|85607|0.143|25|1.18|85 970|0.07|25|0.503|85 0.1 Hfz 904 0.02 Mak 0.47 Lbg0.2 Hir 625|0.078|25|0.8|85 657|0.117|25|0.875|85 704|0.165|25|0.924|850.04 Hje 905 0.02 Mak 0.37 Lbg 0.02 Hfw 710|0.197|25|1.117|85 0.02 Hfz0.2 Hir 906 0.02 Mal 0.091 Lck 0.051 Hjg 509|0.09|25|3.871|85820|0.024|25|0.542|85 874|0.021|25|0.424|85 907 0.02 Mal 0.086 Lck 0.04Har 510|0.112|25|5|85 603|0.187|25|2.856|85 657|0.214|25|2.689|85 0.1Hir 908 0.02 Mak 0.55 Lbs 0.2 Hfz 704|0.302|25|3.312|85756|0.29|25|3.132|85 909 0.02 Mak 0.48 Lbg 0.04 Hn 653|0.176|25|1.562|85700|0.205|25|1.408|85 0.1 Hfz 910 0.01 Mo 2.28 Lck 0.01 Hbb574|0.162|25|0.992|85 636|0.185|25|1.463|85 0.05 Hje 911 0.02 Mal 0.16Lck 0.04 Hbt 563|0.128|25|2.694|85 664|0.146|25|1.989|85930|0.053|25|0.743|85 0.2 Hir 912 0.02 Mal 0.24 Lck 0.2 Hfz637|0.326|25|2.893|85 1143|0.117|25|0.665|85 0.04 Hdh 913 0.002 Mo 0.12Lck 0.02 Hir 392|0.428|25|2.652|85 726|0.017|25|0.634|85748|0.02|25|0.802|85 0.02 Hjt 914 0.02 Mal 0.14 Lck 0.02 Hdx510|0.202|25|0.477|85 703|0.334|25|2.229|85 756|0.321|25|2.192|85 0.2Hfz 915 0.02 Mal 0.15 Lck 0.04 Hgx 481|0.138|25|0.891|85653|0.205|25|0.982|85 703|0.151|25|0.956|85 0.1 Hje 916 0.01 Mo 0.24 Lbs0.2 Hgi 533|0.141|25|0.742|85 576|0.075|25|1.011|85 917 0.002 Mal 0.0089Lck 0.004 Hfw 531|0.06|25|0.754|85 738|0.013|25|0.163|85 0.04 Hir 9180.02 Mak 1.21 Lbg 0.2 Hje 418|0.245|25|0.116|85 653|0.097|25|1.7|85704|0.128|25|1.712|85 919 0.02 Mal 1.04 Lbs 0.3 Hij675|0.076|25|2.172|85 705|0.096|25|2.73|85 756|0.086|25|2.649|85 9200.02 Mak 0.4 Lbg 0.1 Hfz 663|0.147|25|0.626|85 704|0.163|25|0.718|85754|0.128|25|0.664|85 0.02 Hec 921 0.02 Mak 0.19 Lcn 0.2 Hfz704|0.972|25|3.164|85 757|0.956|25|3.077|85 922 0.02 Mak 0.81 Ls 0.2 Hfz660|0.068|25|1.325|85 703|0.078|25|1.526|85 754|0.065|25|1.421|85 9230.02 Mak 0.075 Lck 0.1 Hfz 501|0.094|25|1.538|85 856|0.073|25|0.551|85948|0.086|25|0.582|85 0.02 Hbs 924 0.01 Mo 1.27 Lck 0.05 Hfz634|0.22|25|2.97|85 688|0.158|25|2.311|85 720|0.202|25|2.76|85 0.2 Hke925 0.04 Mal 0.15 Lck 0.2 Hfz 501|0.107|25|2.23|85 702|0.261|25|1.529|85759|0.173|25|1.499|85 0.025 Hgz 926 0.01 Mo 3.1 Lck 0.1 Hdp595|0.142|25|1.202|85 648|0.242|25|2.702|85 0.1 Hfz 927 0.01 Mo 1.38 Lck0.1 Hei 622|0.226|25|2.31|85 675|0.39|25|4.409|85 690|0.412|25|5|85 0.1Hfz 928 0.02 Mal 0.21 Lck 0.06 Hje 620|0.05|25|0.721|85651|0.067|25|0.84|85 704|0.075|25|0.845|85 929 0.02 Mak 0.2 Lbc 0.2 Hfz705|0.913|25|2.883|85 756|0.91|25|2.812|85 930 0.002 Mak 0.001 Hfz500|0.085|25|1.426|85 800|0.035|25|0.376|85 0.08 Hgi 0.61 Hir 931 0.02Mak 0.72 Lbg 0.04 Hcb 663|0.174|25|1.274|85 0.1 Hfz 932 0.02 Mak 0.49 Lv0.2 Hfz 670|0.212|25|2.176|85 705|0.274|25|2.734|85756|0.254|25|2.626|85 933 0.01 Mo 0.95 Lck 0.1 Hjd 641|0.139|25|2.013|85700|0.34|25|5|85 722|0.273|25|5|85 934 0.04 Mal 0.42 Lck 0.01 Hbs488|0.026|25|0.689|85 653|0.188|25|1.745|85 705|0.165|25|1.705|85 0.2Hje 935 0.02 Mal 0.31 Lck 0.1 Hcn 411|0.414|25|5|85 683|0.09|25|1.654|85736|0.082|25|1.739|85 0.08 Hij 936 0.01 Mo 1.87 Lck 0.02 Hje533|0.567|25|0.926|85 606|0.578|25|1.221|85 658|0.58|25|1.166|85 0.2 Hjy937 0.02 Mak 0.32 Lj 0.2 Hfz 705|1.644|25|3.47|85 756|1.652|25|3.275|85938 0.02 Mak 4.69 Lbr 0.2 Hfz 653|0.756|25|2.094|85702|0.763|25|1.926|85 751|0.67|25|1.739|85 939 0.002 Mo 0.24 Lck 0.02Hir 445|0.082|25|1.341|85 691|0.029|25|0.515|85 776|0.047|25|0.802|850.02 Hke 940 0.02 Mal 0.055 Lck 0.19 Hcs 506|0.121|25|4.519|85677|0.053|25|0.681|85 820|0.021|25|0.801|85 0.12 Hir 941 0.01 Mal 0.064Lck 0.01 Hfv 460|0.205|25|5|85 523|0.066|25|5|85 700|0.043|25|1.161|850.1 Hir 942 0.005 Mo 0.28 Lck 0.023 Har 531|0.193|25|0.43|85564|0.14|25|0.491|85 595|0.098|25|0.401|85 0.1 Hgi 943 0.02 Mak 0.69 Lbg0.01 Hea 500|0.123|25|1.055|85 558|0.122|25|0.958|85636|0.281|25|1.155|85 0.16 Hfz 0.06 Hhh 944 0.01 Mal 0.023 Lck 0.03 Har604|0.175|25|2.131|85 657|0.181|25|1.85|85 1020|0.054|25|0.482|85 0.05Hir 945 0.01 Maf 0.54 Lbg 0.38 Hcb 650|0.098|25|0.543|85 0.028 Hfz 9460.01 Mal 0.041 Lck 0.03 Har 511|0.138|25|5|85 595|0.199|25|2.106|85670|0.189|25|2.011|85 0.2 Hir 947 0.02 Mak 0.16 Lck 0.2 Hfz352|0.786|25|5|85 704|0.158|25|1.993|85 756|0.134|25|1.934|85 948 0.021Mak 0.86 Lbs 0.2 Hfz 663|0.067|25|1.753|85 705|0.083|25|1.992|85756|0.072|25|1.864|85 949 0.02 Mal 0.31 Lck 0.02 Hbv557|0.125|25|0.803|85 636|0.186|25|1.016|85 975|0.073|25|0.347|85 0.1Hfz 950 0.02 Mal 0.106 Lck 0.1 Hfz 657|0.116|25|1.428|85701|0.153|25|1.866|85 756|0.144|25|1.834|85 0.2 Hka 951 0.02 Mak 1 Lr0.2 Hfz 660|0.176|25|1.955|85 703|0.244|25|2.197|85754|0.227|25|2.031|85 952 0.02 Mal 0.91 Lck 0.2 Har 392|0.43|25|0.182|85564|0.074|25|1.325|85 975|0.062|25|0.445|85 0.1 Hik 953 0.02 Mal 0.24Lck 0.02 Har 625|0.148|25|1.516|85 0.06 Hij 0.02 Hke 954 0.01 Mo 1.2 Lbg0.04 Hfz 638|0.171|25|1.679|85 667|0.188|25|1.679|85696|0.182|25|1.535|85 0.35 Hgi 955 0.01 Mo 0.93 Lck 0.07 Hfz587|0.222|25|2.024|85 636|0.283|25|3.35|85 0.1 Hgz 956 0.02 Mal 0.38 Lck0.014 Hgz 485|0.05|25|0.436|85 653|0.185|25|1.604|85705|0.157|25|1.597|85 0.2 Hje 957 0.02 Mal 2.77 Lck 0.02 Hdz506|0.235|25|1.783|85 865|0.068|25|0.418|85 990|0.15|25|0.75|85 0.2 Hfz958 0.01 Mal 0.066 Lck 0.02 Hdp 453|0.245|25|5|85 520|0.066|25|5|85690|0.076|25|1.549|85 0.1 Hir 959 0.02 Mak 0.18 Ldo 0.2 Hfz704|1.259|25|3.539|85 756|1.236|25|3.419|85 960 0.02 Mal 0.15 Lck 0.2Hga 484|0.065|25|0.776|85 641|0.154|25|0.502|85 705|0.085|25|0.421|850.04 Hgz 961 0.02 Mal 0.59 Lck 0.02 Hrb 412|0.997|25|0.351|85541|0.179|25|1.43|85 572|0.214|25|1.602|85 0.04 Hje 962 0.01 Mo 0.03 Lbh0.15 Hgi 535|0.289|25|0.921|85 572|0.249|25|1.255|85 963 0.02 Mak 1.1Lbg 0.06 Hfw 620|0.302|25|1.78|85 0.1 Hje 964 0.02 Mak 0.83 Lw 0.2 Hfz704|0.405|25|3.312|85 756|0.396|25|3.169|85 965 0.02 Mak 1.1 Lbg 0.16Hfz 642|0.169|25|1.439|85 686|0.187|25|1.359|85 1028|0.102|25|0.63|850.02 Hke 966 0.01 Mo 0.95 Lck 0.15 Hgh 534|0.151|25|0.795|85575|0.108|25|1.058|85 967 0.02 Mal 0.33 Lck 0.01 Hbt529|0.068|25|0.747|85 630|0.171|25|0.649|85 973|0.081|25|0.377|85 0.01Hbu 0.2 Hfz 968 0.008 Mo 3.3 Lbg 0.12 Hjg 613|0.145|25|1.773|85670|0.141|25|1.869|85 717|0.076|25|1.342|85 0.12 Hjx 969 0.0052 Mo 0.16Lck 0.04 Hhj 615|0.06|25|0.524|85 661|0.049|25|0.49|85 0.04 Hik 970 0.02Mal 0.74 Lck 0.03 Hb 330|0.282|25|2.278|85 384|2.779|25|1.823|85584|0.091|25|0.166|85 971 0.02 Mak 1.13 Lbg 0.02 Hea479|0.138|25|0.842|85 980|0.129|25|0.379|85 0.16 Hje 972 0.02 Mak 0.037Hcw 704|0.313|25|1.023|85 756|0.31|25|0.981|85 0.2 Hfz 973 0.02 Mal 0.11Lck 0.02 Hnr 525|0.222|25|2.695|85 634|0.208|25|0.612|85995|0.127|25|1.025|85 0.06 Hij 974 0.02 Mal 0.085 Lck 0.08 Hff632|0.117|25|1.367|85 700|0.132|25|1.14|85 0.04 Hij 975 0.02 Mal 0.14Lbt 0.058 Hs 415|0.912|25|1.7|85 976 0.02 Mal 0.28 Lck 0.01 Hbt509|0.093|25|0.754|85 620|0.204|25|0.703|85 970|0.109|25|0.429|85 0.2Hfz 0.01 Hgz 977 0.01 Mal 0.53 Lck 0.01 Hdy 457|0.645|25|5|85636|0.066|25|0.476|85 940|0.05|25|0.535|85 0.02 Hir 0.01 Hke 978 0.01 Mo0.76 Lbg 0.019 Hir 559|0.13|25|0.526|85 745|0.004|25|0.131|85 0.033 Hiu979 0.02 Mal 0.093 Lck 0.06 Hik 580|0.078|25|0.837|85621|0.152|25|1.207|85 704|0.207|25|1.101|85 0.52 Hkh 980 0.02 Mal 0.28Lck 0.1 Hje 400|0.187|25|0.11|85 653|0.092|25|1.293|85704|0.095|25|1.308|85 981 0.02 Mal 0.4 Lck 0.02 Hdm631|0.123|25|1.782|85 1137|0.064|25|0.404|85 1184|0.063|25|0.383|85 0.2Hfz 982 0.02 Mal 0.2 Lck 0.02 Hbb 500|0.118|25|0.941|85705|0.484|25|0.785|85 937|0.095|25|0.475|85 0.2 Hje 983 0.01 Mo 2.6 Lbg0.15 Hgh 534|0.297|25|0.82|85 575|0.223|25|1.07|85 984 0.02 Man 0.32 Lck0.04 Hfz 585|0.062|25|0.932|85 648|0.098|25|0.959|85993|0.043|25|0.296|85 0.12 Hhh 0.2 Hir 985 0.02 Mal 0.25 Lck 0.04 Hbt549|0.13|25|1.187|85 610|0.179|25|1.242|85 973|0.084|25|0.524|85 0.1 Hfz986 0.01 Mo 3.22 Lck 0.02 Hbt 577|0.252|25|1.706|85 611|0.369|25|2.47|85632|0.337|25|2.343|85 0.05 Hje 987 0.01 Maf 0.062 Ldd 0.062 Hea496|0.117|25|0.608|85 1000|0.09|25|0.238|85 0.45 Hfz 988 0.01 Mo 2.37Lck 0.02 Hdy 550|0.166|25|0.787|85 588|0.314|25|1.333|85637|0.477|25|1.88|85 0.053 Hil 989 0.02 Mal 0.23 Lck 0.02 Hea499|0.146|25|2.001|85 882|0.076|25|0.517|85 1000|0.149|25|0.801|85 0.16Hfz 990 0.02 Mal 0.14 Lbt 0.058 Hs 420|1.062|25|2.789|85 991 0.02 Mal0.07 Lf 0.1 Har 588|0.312|25|2.45|85 622|0.338|25|2.241|85994|0.112|25|0.654|85 0.06 Hij 992 0.002 Mo 0.31 Lck 0.02 Hir448|0.063|25|1.255|85 689|0.022|25|0.495|85 778|0.033|25|0.741|85 0.02Hjr 993 0.005 Mal 0.016 Lck 0.01 Hfw 533|0.093|25|1.689|85740|0.027|25|0.351|85 0.05 Hir 994 0.01 Mo 0.36 Lck 0.1 Hir373|0.348|25|5|85 717|0.172|25|3.703|85 753|0.116|25|3.419|85 0.1 Hkf995 0.01 Mo 1.19 Lck 0.1 Har 560|0.42|25|0.871|85 996 0.02 Mak 2.45 Lbg0.053 Hfo 583|0.135|25|0.864|85 643|0.101|25|0.694|851051|0.077|25|0.303|85 0.087 Hje 997 0.02 Mak 1.9 Lbg 0.16 Hje593|0.134|25|1.575|85 645|0.171|25|1.627|85 1070|0.096|25|0.618|85 0.2Hke 998 0.01 Mo 1.5 Lck 0.02 Hs 624|0.202|25|1.571|85663|0.156|25|1.23|85 735|0.162|25|1.325|85 0.02 Hfz 999 0.02 Mal 0.08Lck 0.1 Hac 607|0.116|25|0.595|85 661|0.134|25|0.663|85697|0.115|25|0.615|85 0.06 Hij 1000 0.02 Mal 0.22 Lck 0.063 Hcj595|0.101|25|1.059|85 645|0.129|25|1.126|85 1100|0.085|25|0.395|85 0.06Hik 1001 0.01 Mo 1.48 Lck 0.04 Hik 566|0.078|25|0.96|85623|0.098|25|1.413|85 653|0.096|25|1.516|85 0.02 Hio 1002 0.002 Mal0.0089 Lck 0.002 Hdm 391|0.13|25|2.33|85 460|0.038|25|1.16|85519|0.017|25|0.723|85 0.04 Hir 0.2 Hkf 1003 0.011 Mak 1.6 Lbg 0.3 Hhh537|0.032|25|0.484|85 606|0.061|25|0.573|85 975|0.04|25|0.245|85 0.054Hje 1004 0.002 Mo 0.1 Lck 0.002 Hci 392|0.088|25|2.737|85667|0.014|25|0.304|85 748|0.032|25|0.923|85 0.02 Hir 1005 0.02 Mal 0.14Lck 0.005 Hea 499|0.23|25|0.987|85 705|0.254|25|1.78|85757|0.238|25|1.759|85 0.2 Hfz 1006 0.01 Mzz 2.9 Lbg 0.04 Hje545|0.334|25|0.969|85 600|0.295|25|1.612|85 0.15 Hgh Solvent =N,N-Dimethylacetamide 1007 0.01 Mo 1 Lbg 0.15 Hgi 533|0.283|25|0.637|85577|0.189|25|0.772|85 Solvent = Poly(ethylene glycol) of ˜400 averagemolecular weight 1008 0.015 Maf 0.68 Hfz 666|0.155|25|1.572|85703|0.216|25|1.79|85 757|0.214|25|1.618|85 Solvent = Propylene Carbonate1009 0.01 Mo 0.08 Lbg 0.15 Hgi 535|0.288|25|0.946|85571|0.224|25|1.271|85 1010 0.02 Mak 0.19 Lch 0.2 Hfz704|0.279|25|2.698|85 757|0.262|25|2.665|85 1011 0.02 Mak 0.18 Lcg 0.2Hfz 704|0.48|25|2.899|85 756|0.47|25|2.839|85 1012 0.01 Mh 0.03 Lu 0.69Hfz 509|0.542|25|0.529|75 666|0.807|25|2.686|75 724|1.392|25|5|75Solvent = Tetra(ethylene glycol) 1013 0.01 Mo 0.2 Hjx546|0.17|25|0.371|85 586|0.151|25|0.436|85 631|0.128|25|0.405|85 Solvent= 85% Gamma Butyrolactone, 15% Water by weight 1014 0.009 Mq649|0.088|25|1.13|85 Solvent = 76.6% Gamma Butyrolactone, 23.4% Water byweight 1015 0.013 Mr 0.057 Hfz 575|0.12|25|2.569|85635|0.096|25|2.743|85 963|0.431|25|1.122|85 Solvent = 54% GammaButyrolactone, 46% Water by weight 1016 0.003 Mq 0.08 Hfz580|0.144|25|1.053|85 636|0.097|25|1.152|85 Solvent = 90% GammaButyrolactone, 10% Glycerol by weight 1017 0.0009 Mv 0.014 Hje475|0.102|25|0.82|85 Solvent = 83% Gamma Butyrolactone, 17% Toluene byweight 1018 0.02 Mak 0.13 Lck 0.2 Hfz 704|0.226|25|2.844|85756|0.213|25|2.781|85 Solvent = 83% Diethylene Glycol, 17% Water byweight 1019 0.016 Mq 0.18 Hfz 572|0.158|25|1.241|85878|0.679|25|1.309|85 964|0.601|25|1.276|85 Solvent = 86% DiethyleneGlycol, 14% Water by weight 1020 0.008 Mq 0.188 Hfz580|0.126|25|1.094|85 968|0.382|25|0.779|85 Solvent = 82% DiethyleneGlycol, 18% Water by weight 1021 0.027 Mt 0.2 Hfz 877|1.007|25|1.716|85957|0.886|25|1.693|85 1155|0.566|25|1.201|85 Solvent = 78% DiethyleneGlycol, 22% Water by weight 1022 0.027 Mq 0.18 Hfz 575|0.123|25|1.277|85880|0.938|25|1.957|85 Solvent = 94% Propylene Carbonate, 6% Water byweight 1023 0.006 Mq 638|0.213|25|3.299|85 Solvent = 67% Poly(ethyleneglycol) of ˜400 average molecular weight, 33% Water by weight 1024 0.009Mq 0.28 Hfz 560|0.157|25|0.898|85 969|0.402|25|0.693|85 Solvent = 84%Diethylene Glycol, 16% Water by weight 1025 0.008 Mq 0.183 Hfz575|0.129|25|0.992|85 968|0.327|25|0.66|85Key

The following materials were obtained from commercial sources orprepared as described below.

Ma=Bis(1-ethyl-1H-benzimidazole)diiodonickel(II)

To a flask were added 4.0 g nickel acetate tetrahydrate and 216 mln-butanol. The mixture was heated to 70 C under nitrogen and 7.9 g 57%hydroiodic acid were added. Following distillation of 60 ml to removewater and acetic acid, 5.4 g of 1-ethylbenzimidazole were added and thereaction mixture was cooled to 15 C. The crystalline precipitate wasfiltered off, washed with 10 ml of 2-propanol and dried giving 4.8 g ofdark green crystals.

Mb=Diiodobis(tricyclohexylphosphine)nickel(II)

To a flask were added 1.0 g nickel acetate tetrahydrate and 55 mln-butanol. The mixture was heated to 70 C under nitrogen and 2.0 g 57%hydroiodic acid was added. Following distillation of 15 ml to removewater and acetic acid, a solution of 2.6 g of tricyclohexylphosphine in25 ml n-butanol under nitrogen was added to the reaction mixture.Following cooling to 5 C, the crystalline precipitate was filtered,washed with 5 ml of n-butanol and dried giving 2.0 g of reddish browncrystals.

Me=Dibromobis(triphenylphosphine)nickel(II)

To a flask were added 3.0 g nickel bromide trihydrate and 75 mln-butanol. The mixture was heated to 115 C under nitrogen and 5.8 g oftriphenylphosphine were added. Following distillation of 13 ml to removewater, the reaction mixture was cooled to 22 C. The crystalline solidwas filtered, washed with 5 ml of 2-propanol and dried giving 7.3 g ofdark green crystals.

Mf=Diiodobis(triphenylphosphine)nickel(II)

To a flask were added 39.8 g nickel acetate tetrahydrate and 1800 mln-butanol. The solution was heated to 70 C under nitrogen and 75.4 g 57%hydroiodic acid was added. Following distillation of 625 ml to removewater and acetic acid, a solution of 92.3 g of triphenylphosphine in 910ml n-butanol at 70 C was added under nitrogen to the reaction mixture.Following cooling to 22 C, the crystalline solid was filtered, washedwith 100 ml of 2-propanol, then 50 ml 2-propanol and dried giving 121.9g of dark brown plates.

Mh=Cobalt (II) Bromide

Mi=Cobalt (II) Chloride

Mo=Cobalt (II) Tetrafluoroborate hexahydrate

Mq=Copper (II) Bromide

Mr=Copper (II) Bromide Dihydrate

Mt=Copper (II) Chloride Dihydrate

Mv=Copper (II) Nitrate 2.5 Hydrate

Mac=Dibromobis(1-ethyl-1H-benzimidazole)nickel(II)

To a flask were added 709 g nickel bromide trihydrate and 16 Ln-butanol. The mixture was heated to 90 C under nitrogen and 760 g of1-ethylbenzimidazole were added. Following distillation of 1.9 L toremove water, the reaction mixture was cooled to 40 C. The crystallinesolid was filtered, washed with 1 L of 2-propanol, then 500 ml of2-propanol and dried giving 1246 g of bright blue crystals.

Maf=Nickel (II) Bromide Hexahydrate

Maj=Nickel (II) Iodide Hexahydrate

Mak=Nickel (II) Nitrate Hexahydrate

Mal=Nickel (II) Perchlorate Hexahydrate

Man=Nickel (II) Tetrafluoroborate Hexahydrate

Mao=Bis(acetylacetonato)nickel(II)

Mas=Nickel (II) bis(diisobutyldithiophosphinate)

0.55 g Nickel(II) perchlorate hexahydrate was dissolved in 0.5 ml ofwater. 0.60 g of a 50% sodium di(isobutyl)dithiophosphinate watersolution and another 2.5 ml water were added. A dark purple precipitateformed immediately. The precipitate was collected by vacuum filtrationand washed with three 5 ml portions of water. The precipitate was driedat 50 C in a vacuum oven.

Mat=Dibromobis[2-ethyl-2-(hydroxymethyl)propane-1,3-diol]nickel(II)

To a flask were added 7.0 g of nickel acetate tetrahydrate, 130 ml ofn-butanol, and 9.9 g of 48% hydrobromic acid. After distilling off 100ml of solvent, 8.3 g of trimethylolpropane were added and the reactionmixture was cooled to 50 C. Following a slow addition of 90 ml ofhexane, the mixture was cooled to 5 C and the crystalline solid wasfiltered, washed with 10 ml of hexane, and dried giving 11.8 g of lightblue crystals.

Mbn=Tetrabutylammonium triiodo(triphenylphosphine)nickelate(II)

To a flask were added 4.2 g of nickel iodide hexahydrate and 25 ml of2,2-dimethoxypropane. This mixture was stirred under nitrogen at 22 Cfor 1.5 hours, when 50 ml of diethylether were added. After stirring forseveral minutes, the liquids were decanted away from the solids, and thesolids were rinsed twice with 25 ml of diethylether. To the solids wereadded 12 ml n-butanol and after heating to 40 C, the mixture wasfiltered. To the resulting solution, 3.7 g of tetrabutylammonium iodidewere added along with 2.6 g of triphenylphosphine, and the mixture wasstirred at 40 C for 16 hours. After cooling to 22 C, the product wasfiltered and washed with 20 ml of tert-butyl methyl ether and dried,resulting in 3.5 g of a brown solid.

Mbo=Tetrabutylammonium tetraiodonickelate(II)

To a flask were added 50 g of nickel acetate tetrahydrate, 155 gtetrabutylammonium iodide, 650 ml of n-butanol, and 136 g of 47%hydroiodic acid. The mixture was distilled under a slow stream ofnitrogen until 500 ml of solvent was removed. After cooling the mixtureto 50 C, 200 ml tert-butyl methyl ether were added followed by seedcrystals. Following a slow addition of 600 ml of tert-butyl methylether, the mixture was cooled to 22 C and the solid was filtered, washedwith 100 ml of tert-butyl methyl ether, and dried giving 182 g of a redsolid.

Mzz=Cobalt(II) Nitrate Hexahydrate

La=1,1-Bis(hydroxymethyl)cyclopropane

Lb=1,2,4-Butanetriol

Lc=1,2-Phenylenedimethanol

Ld=1,2-Hexanediol

Le=1,2-Propanediol

Lf=Cis,cis-1,3,5-cyclohexanetriol dihydrate

Lh=1,3-Butanediol

Li=1,3-Cyclohexanediol

Lj=2,5-Bis(hydroxymethyl)-1,4-dioxane-2,5-diol

Lk=1,3-Propanediol

Lm=1,4-Dioxane

Lp=18-Crown-6

Lq=1-Ethyl-1H-benzimidazole

To a flask were added 100 g benzimidazole, 44 g sodium hydroxide, 320 mlwater and 480 ml tetrahydrofuran and the mixture was stirred undernitrogen. 157 g Diethyl sulfate were added slowly, maintaining atemperature of 40 C. After 2 hrs at 40 C, the reaction was quenched withslow addition of 100 ml concentrated hydrochloric acid. After washingwith 150 ml hexane, the mixture was basified with 50 g sodium hydroxideand extracted with 275 ml ethyl acetate, then 225 ml ethyl acetate. Thesolvent was removed, leaving an orange oil, which was distilled underfull vacuum to give 109.4 g clear colorless oil.

Lr=2,2,4-Trimethyl-1,3-Pentanediol

Ls=2,2-Dibutyl-1,3-Propanediol

Lt=2,2-Diethyl-1,3-Propanediol

Lu=2,2′-Bipyridine

Lv=2,3-Butanediol

Lw=2,3-Dimethyl-2,3-Butanediol

Ly=2,4-Pentanediol

Lab=2-Bromo-2-Nitro-1,3-Propanediol

Lac=2-Butyl-2-Ethyl-1,3-Propanediol

Lad=2-Ethyl-1,3-Hexanediol

Lae=2-Methyl-1,3-Propanediol

Laf=2-Methyl-2,4-Pentanediol

Lag=2-Methyl-2-Propyl-1,3-Propanediol

Lah=2-Methylenepropane-1,3-diol

Lai=2-Phenyl-1,2-Propanediol

Laj=2-Phenyl-1,3-Propanediol

Lal=Cyclohex-3-ene-1,1-diyldimethanol

Lao=3-Methyl-1,3,5-Pentanetriol

Lap=3-Phenoxy-1,2-Propanediol

Laq=3-Phenyl-1-propanol

Lar=4,4′-Dimethoxy-2,2′-bipyridine

Lav=2-[Bis(2-hydroxyethyl)amino]-2-(hydroxymethyl)propane-1,3-diol

Lax=Diethylene glycol

Laz=Di(Trimethylolpropane)

Lbc=3,3′-Oxydipropane-1,2-diol

Lbd=Dimethyl sulfoxide

Lbf=Ethanol

Lbg=Ethylene Glycol

Lbh=Glycerol

Lbl=Lithium Salicylate

Lbm=Lithium Trifluoroacetate

Lbo=Methanol

Lbq=N,N-Dimethylformamide

Lbr=2,2-Dimethylpropan-1-ol

Lbs=Neopentyl Glycol

Lbt=N—Propyl-N-pyridin-2-ylpyridin-2-amine

To a flask were added 5.0 g 2,2′-dipyridiylamine, 4.9 g of pulverizedpotassium hydroxide and 45 ml of N,N-dimethylformamide. After stirringfor 1 hour under nitrogen, the mixture was cooled to 5 C and 5.0 g of1-iodopropane were added. The mixture was allowed to warm to 22 C andstirred for 5 hours. After quenching with 45 ml water, the product wasextracted with ether and washed twice with water. Following removal ofsolvent, the product was purified by silica gel chromatography using 40%ethyl acetate in hexane to give 4.8 g of nearly colorless oil.

Lbu=Pentaethylene glycol

Lbv=Pentaerythritol

Lbw=Pentaerythritol ethoxylate

Lcc=Tetrahydropyran-2-methanol

Lcd=Tributylphosphine oxide

Lcg=2-(Hydroxymethyl)-2-propylpropane-1,3-diol

A solution 15 ml water and 6 g sodium hydroxide was prepared in a flaskand cooled to 0-5 C under nitrogen. Formaldehyde, (37%), 34.4 g, wasadded drop-wise with vigorous stirring, while keeping temperature below10 C. Valeraldehyde, 10.3 g, was added in small portions. The reactionwas heated to 60 C for five hours, then saturated with sodium chlorideand extracted with 3×50 ml ether. The ether layer was dried over sodiumsulfate, filtered and the solvent was removed. Methanol, 10 ml, wasadded and the solution was cooled in the freezer for 16 hours. Theproduct was filtered off, washed with a little methanol and dried in avacuum oven.

Lch=2-(Hydroxymethyl)-2-methylpropane-1,3-diol

Lci=2-(Hydroxymethyl)propane-1,3-diol

Lcj=2-(Hydroxymethyl)-2-nitropropane-1,3-diol

Lck=Trimethylolpropane

Lcl=Trimethylolpropane allyl ether

Lcm=Trimethylolpropane ethoxylate

Lcn=Trimethylolpropane propoxylate

Lco=Triphenylphosphine

Lcs=Water

Lcz=Tetrahydrofurfuryl alcohol

Ldc=4-(3-Phenylpropyl)pyridine

Ldd=6-Methyl-2,2′-bipyridine

Ldf=Bis(methylsulfinyl)methane

To a flask were added 4.05 g of methyl(methylthio)methyl sulfoxide and40 ml acetic acid. The mixture was cooled to 5 C under nitrogen and 3.7ml of 30% hydrogen peroxide solution was added slowly. The mixture wasallowed to warm to 22 C and stirred under nitrogen for 16 hours. Afterremoval of most of the acetic acid, the product was purified by silicagel chromatography using 10% methanol in ethyl acetate to 20% methanolin ethyl acetate resulting in 3.0 g of a clear colorless oil as amixture of stereo-isomers.

Ldg=Butyl sulfoxide

Ldh=Tetrahydrothiophene 1-oxide

Ldo=2-Ethyl-2-(hydroxymethyl)butane-1,4-diol

To a flask were added 1.5 g diethyl ethylmalonate and 80 ml oftetrahydrofuran and the solution was cooled to 5 C. 0.38 g Sodiumhydride were added in small portions and the reaction was stirred for 2hours at 22 C. After cooling to 5 C, 1.6 g of ethyl bromoacetate wereadded drop wise and the reaction mixture was allowed to stir at 22 Cunder nitrogen for 16 hours. After quenching with a few drops of water,the solvent was removed and the crude oil was dissolved in 20 mltert-butanol and 0.91 g sodium borohydride were added. The mixture washeated to reflux under nitrogen and 1 ml methanol was added drop wise.After stirring for 30 minutes at reflux, the mixture was cooled to 22 Cand made acidic with slow addition of 3M hydrochloric acid. Followingremoval of solvent, the product was purified by silica gelchromatography using pure ethyl acetate resulting in a clear, colorlessoil, 0.4 g.

Ha=(S)-(−)-1-(2-Diphenylphosphino-1-naphthyl)isoquinoline

Hb=[2-(Dicyclohexylphosphino)ethyl]trimethylammonium chloride

Hc=1-(3-Phenylpropyl)-1H-benzimidazole

To a flask were added 5 g benzimidazole and 75 ml tetrahydrofuran undernitrogen and the solution was cooled to 10 C with stirring. 2.2 g Sodiumhydride were added in small portions and the reaction was stirred for 10minutes. 1-Bromo-3-phenylpropane was added and the reaction mixture washeated to 40 C for 5 hrs. After cooling to 5 C, the reaction wasquenched with slow addition of 100 ml water. After the tetrahydrofuranwas removed of by rotovap, the mixture was extracted with 100 ml ethylacetate and washed with 25 ml water and the solvent was removed on therotovap. The product was purified by column chromatography using 40%ethyl acetate in hexane resulting in a light yellow oil whichcrystallized in the freezer.

Hg=2,2′-Butane-1,1-diylbis(1-propyl-1H-benzimidazole)

2,2′-Methylenebis(1H-benzimidazole)

To a flask were added 20 g polyphosphoric acid. After heating to 90 Cunder nitrogen, a mixture of 5.0 g 1,2-phenylenediamine and 2.4 gmalonic acid were added. The reaction mixture was heated to 180 C for 4hours, then cooled to 150 C and poured into 40 ml water. The mixture wasbasified with aqueous ammonium hydroxide. After cooling to 5 C, theproduct was filtered off and washed with water. The solid was reslurriedin 200 ml hot acetonitrile, cooled, filtered and dried leaving 2.7 g ofa gray solid.

2,2′-butane-1,1-diylbis(1-propyl-1H-benzimidazole)

To a flask were added 0.79 g 2,2′-methylenebis(1H-benzimidazole) and 20ml N,N-dimethylformamide under nitrogen. 0.42 g sodium hydride wereadded in portions and the mixture was stirred 20 minutes. 1.74 g1-iodopropane were added slowly and the mixture was stirred at 22 C for16 hrs. After quenching with the slow addition of 40 ml water, theproduct was extracted with ethyl acetate and washed with water. Solventremoval resulted in an oil which was purified by silica gelchromatography using 25% ethyl acetate in hexane to give 0.9 g of alight yellow oil which crystallized on standing.

Hh=1,1′-Bis(diphenylphosphino)ferrocene

Hk=1,1′-Diethyl-1H,1′H-2,2′-bibenzimidazole

To a flask were added 2.0 g 1-ethyl-1H-benzimidazole and 25 mltetrahydrofuran under nitrogen. To this solution was added 20 mln-butyllitium (1.6M) and the mixture was heated to 60 C for 72 hours.After cooling to 22 C, the reaction was quenched with water andextracted with ethyl acetate. Following solvent removal, the product wasdissolved in 8.5 ml hot ethyl acetate and 20 ml of hexane were added.After cooling to 5 C, the product precipitated and was filtered, washedwith hexane, and dried giving 0.42 g pale yellow solid.

Hl=1,2-Benzisoxazole

Hm=2,2′-(1,2-Phenylene)bis(1-ethyl-1H-benzimidazole)

2,2′-(1,2-Phenylene)bis(1H-benzimidazole)

To a flask were added 50 g polyphosphoric acid. After heating to 90 Cunder nitrogen, a mixture of 2.7 g 1,2-phenylenediamine and 2.1 gphthalic acid were added. The reaction mixture was heated to 180 C for 4hours, then cooled to 130 C and poured into 150 ml water. The mixturewas basified with aqueous ammonium hydroxide. After cooling to 5 C, theproduct was filtered and washed with water. After drying, 3.3 g of agray solid remained.

2,2′-(1,2-Phenylene)bis(1-ethyl-1H-benzimidazole)

To a flask were added 1.5 g 2,2′-(1,2-phenylene)bis(1H-benzimidazole)and 30 ml N,N-dimethylformamide and the mixture was cooled to 5 C undernitrogen. 0.48 g Sodium hydride were added in portions and the reactionmixture was stirred for 20 minutes. 1.9 g Todoethane were added and themixture was allowed to warm to 22 C and was stirred for 1 hour. Themixture was quenched slowly with 50 ml water and cooled to 5 C. Theproduct was filtered and washed with water. The product was dissolved in13 ml hot acetonitrile, cooled, filtered and washed with acetonitrileand dried resulting in 1.2 g of an off-white solid.

Hn=2,2′-ethene-1,2-diyldipyridine

Ho=2,2′-(1,2-phenylene)bis(1,3-benzothiazole)

To a flask were added 50 g polyphosphoric acid. After heating to 90 Cunder nitrogen, a mixture of 3.13 g 2-aminophenol and 2.1 g phthalicacid were added. The reaction mixture was heated to 140 C for 4 hours,then cooled to 90 C and poured into 150 ml water. The mixture wasbasified by adding sodium carbonate in small portions and the productwas extracted with ethyl acetate and washed with water. Followingremoval of solvent, the product was dissolved in a minimum amount of hotethanol and allowed to stand at 22 C for 72 hrs. The solid was filteredand washed with a small amount of ethanol. The product wasrecrystallized from 90% ethanol and dried, resulting in 2.8 g of anoff-white solid.

Hr=1,2-Dimethylimidazole

Hs=1,3-Bis(diphenylphosphino)propane

Hv=1,4,8,11-Tetrathiacyclotetradecane

Hx=1,8-Naphthyridine

Hy=10-Methyl-10H-phenothiazine

Hab=1-Benzyl-2-methyl-1H-benzimidazole

To a flask were added 2.5 g 2-methylbenzimidazole, 3.9 g potassiumcarbonate, 60 ml N,N-dimethylformamide and the mixture was stirred undernitrogen. 3.6 g Benzyl chloride were added and the mixture was heated to60 C for 16 hours. The reaction was quenched with 80 ml water and cooledto 22 C. The product was extracted twice with 50 ml ethyl acetate andwashed with water. Following removal of solvent, the product wasdissolved in 100 ml hexane and washed with two portions of water. Afterdrying the hexane layer over sodium sulfate, the mixture was filteredand stripped down to an orange oil.

Hac=1-Benzyl-2-phenyl-1H-benzimidazole

To a flask were added 3 g 2-phenylbenzimidazole, 2.8 g potassiumcarbonate, 40 ml N,N-dimethylformamide and the mixture was stirred undernitrogen. 3.6 g Benzyl chloride were added and the mixture was heated to75 C for 8 hrs. The reaction was cooled to 50 C and quenched with 40 mlof water and cooled to 5 C. The product was filtered, washed with water.The product was recrystallized by dissolving in 57 ml acetonitrile atreflux and 39 ml water were added. After cooling to 5 C, the product wasfiltered, washed and dried giving 3.1 g.

Had=1-Benzyl-2-pyridin-2-yl-1H-benzimidazole

To a flask were added 2.0 g 2-(2-pyridyl)benzimidazole, 1.8 g potassiumcarbonate, 30 ml N,N-dimethylformamide and the mixture was stirred undernitrogen at 10 C. 1.5 g benzyl chloride were added and the mixtureallowed to warm to 22 C and stirred for 3 hours. Another 0.3 g benzylchloride was added and the reaction was stirred at 22 C for another 16hours. The reaction was quenched with 40 ml water and the product wasfiltered and washed with water. The product was dissolved in 10 mlethanol and 15 ml of water were added. After cooling to 5 C, the productwas filtered, washed and dried resulting in 2.4 g of off-white solid.

Hae=1-Benzyl-2-(benzylsulfanyl)-6-methyl-1H-benzimidazole

To a flask were added 2.0 g 2-mercapto-5-methylbenzimidazole, 4.2 gpotassium carbonate, 30 ml N,N-dimethylformamide and 3.9 g benzylchloride. The reaction mixture was heated to 60 C for 16 hours, thencooled to 50 C and quenched with 60 ml water and cooled to 5 C. Thesolid was filtered and washed with water and then recrystallized bydissolving in 50 ml hot acetonitrile and adding 10 ml of water. Aftercooling to 5 C, the product was filtered, washed and dried resulting in3.5 g white solid as a mixture of the 5-methyl and 6-methyl isomers.

Hag=1-Benzyl-4-methyl-1H-benzimidazole

4-methyl-1H-benzimidazole

To a flask were added 2.0 g 2,3-diaminotoluene, 1.0 g 90% formic acidand 30 ml 5M hydrochloric acid and the mixture was heated to 90 C undernitrogen for 4 hours. After cooling to 22 C, the mixture was basifiedwith aqueous ammonium hydroxide and the product was removed byfiltration and washed with water. The product was purified by columnchromatography using pure ethyl acetate resulting in 1.0 g brown solid.

1-Benzyl-4-methyl-1H-benzimidazole

To a flask were added 1.0 g 4-methyl-1H-benzimidazole, 1.6 g potassiumcarbonate, 25 ml N,N-dimethylformamide and the mixture was stirred undernitrogen. 1.4 g Benzyl chloride were added and the mixture was heated to60 C for 16 hours. Another 0.4 g of benzyl chloride were added and thereaction was heated to 70 C for 24 hours. The reaction was cooled to 50C and quenched with 50 ml water and extracted with ethyl acetate. Afterwashing with water, the solvent was removed and the product was purifiedby column chromatography using a gradient from 40% ethyl acetate inhexane to 75% ethyl acetate in hexane. Following removal of the solvent,the partially crystallized product was dissolved in 20 ml acetonitrileand treated with 0.1 g activated carbon. After refluxing for 20 minutes,the mixture was filtered through celite and the solvent was removedleaving a yellow oil which crystallized on standing, 1.0 g.

Hah=1-Benzyl-1H-benzimidazole

To a flask were added 2 g benzimidazole, 3.5 g potassium carbonate, 20ml N,N-dimethylformamide and the mixture was stirred under nitrogen. 3.2g Benzyl chloride were added and the mixture was heated to 50 C for 16hrs. The reaction was quenched with 40 ml water and 7 ml 3M hydrochloricacid and cooled to 5 C. The product was filtered and washed with water.The product was recrystallized by dissolving in 10 ml 2-propanol atreflux, hot filtered and 30 ml hexane were added. After cooling to 5 C,the product was filtered, washed with hexane and dried giving 1.6 g.

Hai=1-Ethyl-1H-imidazo[4,5-b]pyridine

To a flask were added 0.5 g 4-azabenzimidazole and 10 mlN,N-dimethylformamide and the mixture was cooled to 10 C under nitrogen.0.18 g Sodium hydride were added in portions and the reaction mixturewas stirred for 20 minutes. 0.71 g Diethylsulfate were added and themixture was allowed to warm to 22 C and was stirred for 16 hours. Themixture was quenched slowly with 30 ml 1M hydrochloric acid and theaqueous layer was washed with ethyl acetate. After basification withsodium hydroxide, the product was extracted twice with ethyl acetate anddried over sodium sulfate. Following filtration and solvent removal, theproduct was purified by silica gel chromatography using 5% methanol inethyl acetate to 12% methanol in ethyl acetate. 0.4 g Of an oil wasobtained.

Haj=1-Ethyl-1H-benzimidazole

To a flask were added 100 g benzimidazole, 44 g Sodium hydroxide, 320 mlwater and 480 ml tetrahydrofuran and the mixture was stirred undernitrogen. 157 g Diethyl sulfate were added slowly, maintaining atemperature of 40 C. After 2 hrs at 40 C, the reaction was quenched withslow addition of 100 ml concentrated hydrochloric acid. After washingwith 150 ml hexane, the mixture was basified with 50 g Sodium hydroxideand extracted with 275 ml ethyl acetate, then 225 ml ethyl acetate. Thesolvent was removed, leaving an orange oil, which was distilled underfull vacuum to give 109.4 g clear colorless oil.

Hak=1-Ethyl-2-(1,3-thiazol-4-yl)-1H-benzimidazole

5.0 g Thiabendazole and 1.31 g sodium hydroxide were added to 40 ml oftetrahydrofuran. The white slurry was stirred under nitrogen and 4.6 gof diethylsulfate was added dropwise. The mixture was stirred at 50 Cfor 16 hours. The mixture was quenched with 75 ml of water and thenextracted with 75 ml or ethyl acetate. The organic layer was washed with15 ml of water. Following solvent removal, an off-white solidcrystallized. The solid was recrystallized from 30 ml (2:1, v/v)ethanol/water. The solid was dried under vacuum for 3 hrs at 50 C. 3.7 gof a white solid was obtained.

Ham=2-(1H-Benzimidazol-1-yl)ethanol

To a flask were added 2.3 g benzimidazole and 40 ml tetrahydrofuran andthe mixture was cooled to 10 C under nitrogen. 11.0 g Sodium hydridewere added in portions and the reaction mixture was stirred for 20minutes. 4.0 g 2-Iodoethanol were added and the mixture was heated to 50C for 16 hours. The mixture was quenched slowly with 50 ml water,extracted twice with ethyl acetate and dried over sodium sulfate.Following filtration and solvent removal, the product was purified bysilica gel chromatography using 25% methanol in ethyl acetate. A solidwas obtained that was dissolved in a hot mixture of 10% methanol inethyl acetate, cooled, filtered and dried giving 1.4 g white solid.

Han=2-[2-(Diphenylphosphino)phenyl]-1-methyl-1H-benzimidazole

2-(2-Bromophenyl)-1H-benzimidazole

To a flask were added 80 g methanesulfonic acid and 8 g phosphoruspentoxide and the mixture was heated to 60 C under nitrogen until thesolids had completely dissolved. To this solution was added 2.7 g1,2-phenylene diamine and 5.0 g 2-bromobenzoic acid and the mixture washeated to 100 C for 30 minutes. The mixture was poured onto 300 ml icewater and basified with the addition of small portions of sodiumcarbonate. Following filtration of the solid and washing with water, thecrude product was dissolved in 85 ml hot ethanol, filtered and 9 ml ofwater was added. After cooling to 5 C, the product was filtered andwashed with 50% ethanol and dried, giving 3.85 g off-white solid.

2-(2-Bromophenyl)-1-methyl-1H-benzimidazole

To a flask were added 3.3 g 2-(2-bromophenyl)-1H-benzimidazole and 100ml tetrahydrofuran and the mixture was cooled to 10 C under nitrogen.0.63 g Sodium hydride were added in portions and the reaction mixturewas stirred for 20 minutes. 2.0 g Dimethylsulfate were added and themixture was heated to 22 C for 30 minutes. The mixture was quenchedslowly with 100 ml water, extracted with ethyl acetate and thenextracted into a 1 M hydrochloric acid solution. The solution was washedwith ethyl acetate and then basified with 3M sodium hydroxide. Followingextraction with ethyl acetate and solvent removal, the solid wasdissolved in a hot mixture of 20 ml hexane with 4 ml 2-propanol. Aftercooling to 5 C, the product was filtered, washed with hexane and driedgiving 2.9 g of a white solid.

2-[2-(Diphenylphosphino)phenyl]-1-methyl-1H-benzimidazole

To an oven dried flask that was purged with nitrogen was added 1.5 g2-(2-bromophenyl)-1-methyl-1H-benzimidazole and 50 ml drytetrahydrofuran. The solution was cooled to −70 C and 3.9 ml of a 1.6Msolution of n-butyllithium in hexanes was added drop wise. Afterstirring 1 hour at less than −60 C, 1.4 g chlorodiphenylphosphine wasadded drop wise and the mixture was allowed to warm to 22 C. The mixturewas quenched with 100 ml of nitrogen-purged water and extracted withnitrogen-purged ethyl acetate. Following solvent removal, the solid wasdissolved in 10 ml of hot, nitrogen-purged ethanol and 7 ml ofnitrogen-purged water was added. After cooling to 5 C, the product wasfiltered and washed with 50% ethanol that was nitrogen-purged and driedgiving 1.3 g off-white solid.

Hao=1-Methyl-1H,1′H-2,2′-bibenzimidazole

1H,1′H-2,2′-Bibenzimidazole

To a flask were added 10.8 g 1,2-phenylene diamine, 2.65 ghexachloroacetone and 50 ml ethylene glycol. The mixture was mixed andheat to 55 C under nitrogen and sonicated for 3 hours. After cooling to22 C, the solid was filtered and washed with acetone and dried leaving1.3 g yellow solid.

1-Methyl-1H,1′H-2,2′-bibenzimidazole

To a flask were added 1.2 g 1H, 1′H-2,2′-bibenzimidazole, 0.45 g sodiumhydroxide, 100 ml N,N-dimethylformamide and 1.4 g dimethylsulfate. Themixture was heated to 45 C under nitrogen for 16 hours and another 0.45g sodium hydroxide and 2.8 g dimethylsulfate were added and the mixturewas stirred at 45 C for 24 hours. Another 4.2 g of dimethylsulfate wereadded and the mixture was stirred at 45 C for 24 hours, then cooled to22 C and quenched with 350 ml water. The off-white solid was filteredand washed with water. After dissolving the product in 125 ml hotethanol, 44 ml water were added and the solution was cooled to 5 C,filtered, washed with 50% ethanol and dried leaving 0.5 g white solid.

Haq=1-Methyl-2-pyridone

Har=1-Methyl-1H-benzimidazole

Has=1-Methyl-1H-imidazole

Hat=1-Phenyl-1H-benzimidazole

N-Phenylbenzene-1,2-diamine

To a pressure reaction bottle was added 10 g 2-nitrodiphenylamine, 0.5 g5% palladium on carbon and 100 ml 95% ethanol. The mixture washydrogenated at 22 C and 40 psi hydrogen for 2 hours. Followingfiltration through celite and solvent removal, an oil was obtained thatcrystallized on standing.

1-Phenyl-1H-benzimidazole

To a flask were added crude N-phenylbenzene-1,2-diamine, 9.7 gformamidine acetate and 175 ml 2-methoxyethanol and the mixture washeated to reflux under nitrogen for 30 minutes. After cooling to 22 C,the solvent was removed and the mixture was dissolved in ethyl acetateand washed with water. Following removal of the solvent, the product waspurified by silica gel chromatography using 50% ethyl acetate in hexanegiving a tan oil.

Hau=1-Phenyl-1H-imidazole

Hav=2-Methyl-1-propyl-1H-benzimidazole

To a flask were added 2.0 g 2-methylbenzimidazole and 40 mltetrahydrofuran and the mixture was cooled to 10 C under nitrogen. 0.9 gSodium hydride were added in portions and the reaction mixture wasstirred for 20 minutes. 3.9 g 1-iodopropane were added and the mixturewas heated to 45 C for 6 hours. The mixture was quenched slowly with 40ml water, extracted twice with ethyl acetate and washed with water.Following solvent removal, the product was purified by silica gelchromatography using pure ethyl acetate to 5% methanol in ethyl acetate.A pale yellow oil was obtained.

Haw=2-Phenyl-1-propyl-1H-benzimidazole

To a flask were added 3.0 g 2-phenylbenzimidazole and 60 mltetrahydrofuran and the mixture was cooled to 10 C under nitrogen. 0.41g Sodium hydride were added in portions and the reaction mixture wasstirred for 20 minutes, then cooled to 10 C. 3.1 g 1-iodopropane wereadded and the mixture was heated to 55 C for 16 hours. Another 0.8 g1-iodopropane were added and the temperature was held at 55 C for twohours. The mixture was cooled to 22 C, quenched slowly with 40 ml water,extracted with ethyl acetate and washed with water. Following solventremoval, the product was purified by silica gel chromatography usingstraight 67% ethyl acetate, 24% hexane and 9% methanol. An oil wasobtained.

Hay=1-Propyl-1H-benzimidazole

To a flask were added 2.0 g benzimidazole, 3.5 g potassium carbonate,4.3 g 1-iodopropane and 20 ml N,N-dimethylformamide. The mixture washeated to 45 C under nitrogen for 16 hours and then quenched with 30 mlwater and the product was extracted with ethyl acetate. Followingremoval of the solvent, the product was purified by silica gelchromatography using 66% ethyl acetate in hexane. The brown oil wasagain purified by silica gel chromatography using ethyl acetate, givinga slightly yellow oil 1.5 g.

Haz=N,N-Dimethyl-2-pyridin-2-ylethanamine

Hbb=N-Methyl-2-pyridin-2-ylethanamine

Hbc=2-Pyridin-2-yl-1H-benzimidazole

Hbf=N,N-Dimethyl-1-pyridin-2-ylmethanamine

Hbj=2,1,3-Benzothiadiazole

Hbl=2,2′-Propane-2,2-diylbis(1-propyl-1H-benzimidazole)

2,2′-Propane-2,2-diylbis(1H-benzimidazole)

To a thick walled glass tube was added a mixture of 5.8 g 1,2-phenylenediamine dihydrochloride and 1.5 g malononitrile. The tube wasflame-sealed under full vacuum and heated to 220 C for 1.5 hours causingthe mixture to turn black. After cooling to 22 C, the black material wasadded to 60 ml 1M hydrochloric acid and stirred and heated to 50 C forseveral hours. After adding 150 mg activated carbon, the mixture wasbrought to reflux and filtered through celite. The clear filtrates werebasified with aqueous ammonium hydroxide resulting in a cream coloredsolid which was filtered and washed with water. After re-slurrying thesolid in hot water and filtering, the product was dried resulting in 2.5g.

2,2′-Propane-2,2-diylbis(1-propyl-1H-benzimidazole)

To a flask were added 1.4 g 2,2′-propane-2,2-diylbis(1H-benzimidazole)and 30 ml tetrahydrofuran and the mixture was cooled to 10 C undernitrogen. 0.61 g Sodium hydride were added in portions and the reactionmixture was stirred for 20 minutes. 2.6 g 1-iodopropane were added andthe mixture was stirred at 22 C for 3.5 hours. The mixture was quenchedslowly with 30 ml water and stirred 16 hours. After cooling to 5 C, thesolid was filtered and washed with water and purified by silica gelchromatography using 25% ethyl acetate in hexane to 50% ethyl acetate inhexane. 1.4 g of off-white solid was obtained.

Hbn=2,2′-Propane-2,2-diylbis(1,3-benzothiazole)

To a flask were added 50 g polyphosphoric acid. After heating to 70 Cunder nitrogen, a mixture of 3.13 g 2-aminothiophenol and 1.65 gdimethylmalonic acid was added. The reaction mixture was heated to 150 Cfor 2 hours, then 165 C for 3 hours. After cooling to 80 C, the mixturewas poured into 100 ml water. The slurry was cooled to 5 C, filtered andthe solid was washed with water. The solid was added to a mixture of 20ml ethanol and 210 ml water at 50 C and basified with aqueous ammoniumhydroxide. After cooling to 10 C, the solid was filtered and washed withwater. The solid was dissolved in 50 ml hot ethanol, hot filtered and 5ml water was added and the solution was cooled to 5 C. Followingfiltration, the white solid was washed with 75% ethanol and dried.

Hbs=N-Pyridin-2-ylpyridin-2-amine

Hbt=2,2′-Ethane-1,2-diyldipyridine

To a Pressure reaction bottle was added 6.9 g of2,2′-bis(dipyridyl)ethene, 0.6 g 5% palladium on carbon, and 200 mlethanol. The mixture was purged with hydrogen and then hydrogenatedunder 40 psi hydrogen for 16 hours. The catalyst was filtered off on abed of celite. The solvent was removed and the residue was dissolved in40 ml of hot hexane, and filtered hot. After the addition of seedcrystals and cooling to 10 C, the product was filtered, washed withhexane and dried, resulting in 5.3 g of an off-white solid.

Hbu=2,2′-Methylenedipyridine

To a flask were added 5 g of 2,2′-dipyridylketone, 3.2 g of potassiumhydroxide, 100 ml of diethyene glycol and 3.4 g of hydrazine hydrate.The mixture was heated to 100 C under nitrogen for 1 hour, then heatedto 150 C for 2 hours, and then 180 C for 3 hours. After cooling to 22 C,150 ml of water were added and the mixture was extracted with 150 mlethyl acetate. After washing the ethyl acetate layer twice with 50 ml ofwater, the solvent was removed and the product was purified by silicagel chromatography using 95% ethyl acetate with 5% methanol to give 1.9g of a light yellow oil.

Hbv=2,2′-Propane-1,3-diyldipyridine

To a flask were added 93 g of 2-picoline, 21 g of 2-vinylpyridine, 1 gof sodium and a trace of hydroquinone. The mixture was heated to 130 Cunder nitrogen for 2 hours. After cooling to 22 C, 200 ml of water wereadded and the mixture was extracted with 150 ml diethyl ether. Afterwashing the diethyl ether layer twice with 100 ml of water, and twicewith 50 ml of 10% sodium sulfite, the solvent was removed and theproduct was purified by vacuum distillation to give 7.5 g of a lightyellow oil.

Hbz=2,4,6-Trimethylpyridine

Hca=2,4-Pentanedione

Hcb=2,5-Lutidine

Hcg=1H-Benzimidazol-2-ylmethanol

Hci=2′-(Diphenylphosphino)-N,N-dimethylbiphenyl-2-amine

Hcj=2-(Diphenylphosphino)-6-methylpyridine

Hcn=2-Mercapto-1-methylimidazole

Hco=2-Mercapto-5-methylbenzimidazole

Hcp=Pyridine-2-thiol

Hcq=Pyrimidine-2-thiol

Hcr=2-Methyl-1H-benzimidazole

Hcs=2-Methylbenzothiazole

Hct=1H-Benzimidazol-2-ol

Hcv=Pyridin-2-ylmethanol

Hcw=3-(Diethylamino)-1,2-propanediol

Hcx=3,3-Dimethyl-2,4-pentanedione

Hcz=3,6-Dithia-1,8-octanediol

Hdc=3-Methyl-2,2′-bipyridine

To a flask were added 11.0 g 2-bromo-3-methylpyridine and 10 ml of drytetrahydrofuran. The solution was purged with nitrogen and 34 mgtetrakis(triphenylphosphine)palladium was added followed by 17.4 ml of a0.5M solution of 2-pyridylzinc bromide in tetrahydrofuran. The mixturewas stirred at 22 C for 24 hours, then 40 C for 72 hours. The mixturewas poured into a solution of 5 g EDTA, 2 g sodium carbonate and 40 mlwater. The product was extracted twice with diethylether, washed withwater and dried over sodium sulfate. Following filtration and solventremoval, the product was purified by silica gel chromatography using 48%ethyl acetate, 48% hexane and 4% methanol. A slightly yellow oilremained 0.38 g.

Hde=4,4′-Dimethoxy-2,2′-bipyridine

Hdf=3,4-Dimethoxyaniline

Hdh=Phenyl(pyridin-4-yl)methanone

Hdi=N,N-Dimethylpyridin-4-amine

Hdj=4-Hydroxypyridine

Hdm=4-(3-Phenylpropyl)pyridine

Hdo=4-Pyridinecarboxaldehyde

Hdp=4-Tert-butylpyridine

Hds=5-Hydroxy-2-methylpyridine

Hdt=5-Methoxy-1-methyl-1H-benzimidazole

To a flask were added 2.5 g 5-methoxybenzimidazole and 40 mltetrahydrofuran and the mixture was cooled to 10 C under nitrogen. 0.9 gSodium hydride were added in portions and the reaction mixture wasstirred for 20 minutes. 2.6 g Dimethylsulfate were added and the mixturewas allowed to warm to 22 C and was stirred for 2 hours. The mixture wasquenched slowly with 50 ml water and the tetrahydrofuran was removed bydistillation. The product was extracted twice with ethyl acetate andwashed with water. Following solvent removal, the product was purifiedby silica gel chromatography using 5% methanol in ethyl acetate to 10%methanol in ethyl acetate. 2.2 g Of off-white solid was obtained. 1.6 gOf this product was dissolved in 7 ml hot toluene and 25 ml hexane wereadded along with a seed crystal. After cooling to 5 C, the crystallinesolid was filtered, washed with hexane and dried to give 1.2 g of awhite solid as a mixture of the 5-methoxy and 6-methoxy isomers.

Hdv=8-Methyl-3,4-dihydro-2H-[1,3]thiazino[3,2-a]benzimidazole

To a flask were added 2 g 2-mercapto-5-methylbenzimidazole, 4.2 gpotassium carbonate, 4.0 g 1,3-diiodopropane and 60 mlN,N-dimethylformamide. The mixture was heated to 50 C under nitrogen for5 hours and then cooled to 22 C. The reaction was quenched with 100 mlwater and the product was extracted twice with ethyl acetate and washedtwice with water. Following removal of the solvent, the product wasrecrystallized by dissolving in a hot mixture of 50 ml hexane with 10 ml2-propanol. After cooling to 5 C, the product was filtered, washed withhexane and dried giving 0.63 g of an off-white solid.

Hdx=6,6′-Dibromo-2,2′-bipyridine

Hdy=6,6′-Dimethyl-2,2′-bipyridine

Hdz=6-Butyl-6′-methyl-2,2′-bipyridine

2-(Benzyloxy)-6-chloropyridine

To a flask were added 5.0 g 6-chloro-2-hydroxypyridine, 5.3 g potassiumcarbonate and 75 ml N,N-dimethylformamide. After cooling to 5 C undernitrogen, 5.9 g of benzyl chloride were added drop wise and the reactionmixture was warmed to 60 C for 3 hours. After cooling to 10 C, thereaction mixture was quenched with 75 ml of water and the product wasextracted with ethyl acetate and washed with water. Following solventremoval, the product was purified by silica gel chromatography using 5%ethyl acetate in hexane to give a clear colorless oil 7.9 g.

2-(Benzyloxy)-6-butylpyridine

To a flask were added 2.0 g 2-(benzyloxy)-6-chloropyridine, 5.0 ml1-methyl-2-pyrrolidinone and 50 ml of dry tetrahydrofuran. After coolingto 5 C under nitrogen, 0.16 g iron(III) acetylacetonate were addedfollowed by drop wise addition of 8.5 ml of a 2M solution ofbutylmagnesium bromide in tetrahydrofuran. After stirring for 1 hour at22 C, the reaction was cooled to 10 C and quenched with 20 ml aqueousammonium chloride. The mixture was diluted with water and extracted withhexane. After washing with water and removal of solvent, the product waspurified by silica gel chromatography using 10% ethyl acetate in hexaneto give 1.6 g of an oil.

6-Butylpyridin-2-ol

To a pressure reaction bottle were added 1.6 g2-(benzyloxy)-6-butylpyridine, 0.2 g 5% palladium on carbon and 50 mlethanol. The mixture was hydrogenated at 22 C and 40 psi hydrogen for 16hours. Following filtration through celite and solvent removal, an oilwas obtained that crystallized on standing to give 0.9 g.

6-Butylpyridin-2-yl trifluoromethanesulfonate

To a flask were added 0.9 g 6-butylpyridin-2-ol and 10 ml pyridine andthe mixture was cooled to 10 C under nitrogen. 1.85 gtrifluoromethanesulfonic anhydride were added slowly and the reactionmixture was allowed to warm to 22 C and stirred for 16 hours. Aftercooling to 5 C, the mixture was quenched with 20 ml of water andextracted twice with hexane. After drying over sodium sulfate, thesolution was filtered and the solvent was removed. Purification bysilica gel chromatography using 5% ethyl acetate in hexane resulted in1.2 g of a clear colorless oil.

6-Butyl-6′-methyl-2,2′-bipyridine

To a flask were added 1.2 g 6-butylpyridin-2-yltrifluoromethanesulfonate, 0.36 g lithium chloride and 10 ml drytetrahydrofuran. Addition of 12 ml of a 0.5M solution of6-methyl-2-pyridylzinc bromide in tetrahydrofuran was followed byaddition of 242 mg of tetrakis(triphenylphosphine)palladium. Thereaction was heated to reflux under nitrogen for 16 hours. The reactionwas cooled to 22 C and quenched by adding a solution of 6 g of ethylenediamine tetraacetic acid in 40 ml water pH adjusted to 8 with aqueoussodium bicarbonate. 50 ml Hexane and 20 ml ethyl acetate were added andthe mixture was stirred for one hour before the aqueous layer wasremoved and the organic layer was dried over sodium sulfate. Afterfiltration and solvent removal, the product was purified by silica gelchromatography using 5% ethyl acetate in hexane to give 0.7 g clearcolorless oil.

Hea=6-Methyl-2,2′-bipyridine

Hec=Quinolin-8-ol

Hee=Acetylcholine Chloride

Heg=Anthranil

Heh=Benzimidazole

Hei=Benzothiazole

Hej=Benzoxazole

Hen=Benzyltrimethylammonium Chloride

Heo=2,2′-Ethane-1,2-diylbis(1H-benzimidazole)

To a flask were added 3 g of 1,2-phenylene diamine, 1.6 g of succinicacid, and 30 ml of 4M hydrochloric acid. The mixture was heated toreflux under nitrogen for 22 hours, and then cooled to 22 C. The solidwas filtered, washed with a little water and dissolved in a warm mixtureof 30 ml of acetone and 40 ml of water. Enough ammonium hydroxide wasadded to basify the mixture, and after cooling to 22 C, the product wasfiltered and washed with 20 ml of 50% acetone and dried, resulting in alight pink solid.

Hes=Choline chloride

Heu=1-Pyridin-2-yl-N-(pyridin-2-ylmethyl)methanamine

Hew=Dipyridin-2-ylmethanone

Hez=N,N′-Bis[phenylmethylene]ethane-1,2-diamine (mixture of cis/transisomers)

Hfc=Diethylphenylphosphine

Hfd=2-(Diphenylphosphino)pyridine

Hfe=Diphenylphosphine oxide

Hff=Di-tert-butylphosphine oxide

To a flask were added 1.0 g of di(tert-butyl)chlorophosphine and 5 ml ofdichloromethane under nitrogen. After slow addition of 0.25 g of water,the mixture was stirred at 22 C for 30 minutes and the solvent wasremoved leaving a solid. After purification by sublimation, 0.9 g of awhite solid was obtained.

Hfi=Ditetrabutylammonium malonate

To a flask were added 3.1 g malonic acid, 24.6 g of a 55-60% solution oftetrabutylammonium hydroxide in water, 13 ml water and 75 ml 2-propanol.After heating to 50 C under nitrogen for 1 hour, the solvent was removedand another 30 ml of 2-propanol were added and removed by distillationunder reduced pressure. After drying, an oil was obtained.

Hfj=Ditetrabutylammonium phenylphosphonate

To a flask were added 2.0 g phenylphosphonic acid, 111.0 g of a 55-60%solution of tetrabutylammonium hydroxide in water and 30 ml 2-propanol.After heating to 50 C under nitrogen for 1 hour, the solvent was removedand another 30 ml of 2-propanol were added and removed by distillationunder reduced pressure. After drying, a pinkish oil was obtained.

Hfl=Ditetrabutylammonium succinate

To a flask were added 3.5 g succinic acid, 26.4 g of a 55-60% solutionof tetrabutylammonium hydroxide in water, 13 ml water and 75 ml2-propanol. After heating to 50 C under nitrogen for 1 hour, the solventwas removed and another 75 ml of 2-propanol were added and removed bydistillation under reduced pressure. After drying, an oil was obtained.

Hfo=Ethyldiphenylphosphine

Hfr=Imidazo[1,2-a]pyridine

Hfs=Imidazo[1,5-a]pyridine

To a flask were added 2.0 g of 2-(aminomethyl)pyridine, 0.12 g oftetrabutylammonium bromide, 5.7 g of chloroform, and 30 ml1,2-dimethoxyethane. While stirring under nitrogen, 40 ml of 40% aqueousSodium hydroxide was added and the mixture was heated to 50 C for 4.5hours. After cooling to 22 C, the mixture was extracted twice with ethylacetate, and the ethyl acetate layer was dried over sodium sulfate.After filtration and solvent removal, the product was purified by silicagel chromatography using straight ethyl acetate to 5% acetonitrile inethyl acetate resulting in a brown oil which crystallized on standing.The product was sublimed to give 0.36 g of a yellow solid.

Hfv=Isoquinoline

Hfw=Lepidine

Hfx=Lithium Acetate

Hfy=Lithium Benzoate

Hfz=Lithium Bromide

Hga=Lithium Chloride

Hgc=Lithium Diphenylphosphinate

To a flask were added 1.0 g diphenylphosphinic acid, 182 mg lithiumhydroxide monohydrate, 10 ml of water and 30 ml 2-propanol. The mixturewas heated to 70 C under nitrogen until a clear solution was obtained.The mixture was cooled and the solvent was removed under reducedpressure and the product was slurried in a small amount of 2-propanol,filtered and washed with 2-propanol. After drying, a white solid wasobtained.

Hgh=Lithium Salicylate

To a flask were added 10.0 g salicylic acid, 2.9 g lithium hydroxidemonohydrate, 20 ml of water and 100 ml 2-propanol. The mixture washeated to 50 C for 1.5 hours and then cooled and the solvent was removedunder reduced pressure. The product was slurried in 25 ml diethyl ether,filtered and washed with diethyl ether. After drying, 7.0 g of a whitesolid was obtained.

Hgi=Lithium Trifluoroacetate

Hgk=N,N,N′,N′-Tetramethylpropane-1,3-diamine

Hgm=N,N,N′,N′-Tetramethylethylenediamine

Hgp=N,N-Dipyridin-2-ylacetamide

To a flask were added 2,2′-dipyridylamine and 12 ml acetic anhydride.The mixture was heated to 110 C under nitrogen for 5 hours and cooled to22 C. After quenching with a slow addition of aqueous sodiumbicarbonate, the mixture was made basic with the addition of smallportions of sodium carbonate. The product was extracted with ethylacetate and after removal of solvent, it was purified by silica gelchromatography using 65% ethyl acetate in hexane to give 0.8 g of anoil.

Hgr=2,9-Dimethyl-1,10-phenanthroline hydrate

Hgt=N-Methyl-N-pyridin-2-ylpyridin-2-amine

To a flask were added 1.0 g 2,2′-dipyridiylamine, 1.0 g of pulverizedpotassium hydroxide and 15 ml of N,N-dimethylformamide. After stirringfor 1 hour under nitrogen, the mixture was cooled to 5 C and 0.9 g ofiodomethane were added. The mixture was allowed to warm to 22 C andstirred for 16 hours. After quenching with 15 ml water, the reaction wasextracted twice with diethyl ether and washed with water. Followingremoval of solvent, the product was purified by silica gelchromatography using 35% ethyl acetate in hexane to give 0.16 g of anoil.

Hgu=N,6-Dimethyl-N-pyridin-2-ylpyridin-2-amine

To a flask were added 0.75 g 2-(methylamino)pyridine, 1.0 g2-bromo-6-methylpyridine, 0.95 g sodium tert-butoxide, 0.16 g1,1′-bis(diphenylphosphino)ferrocene and 50 ml toluene. The mixture waspurged thoroughly with nitrogen and 0.14 g oftris(dibenzylideneacetone)d2-propanollladium(0) was added and themixture was heated to 80 C. under nitrogen for 16 hours. After coolingto 22 C and quenching with 50 ml water, the product was extracted twicewith ethyl acetate and washed twice with water. After filtration andsolvent removal, the product was purified by silica gel chromatographyusing 35% ethyl acetate in hexane resulting in an orange oil. This wasdissolved in 75 ml tert-butyl methyl ether and extracted into 75 ml 1Mhydrochloric acid. After basification with 3M sodium hydroxide solution,the product was extracted with 75 ml tert-butyl methyl ether. Followingremoval of solvent, 1.1 g of a yellow oil was obtained.

Hgw=N-Octadecyl-N-pyridin-2-ylpyridin-2-amine

To a flask were added 1.0 g 2,2′-dipyridylamine, 1.0 g of pulverizedpotassium hydroxide and 15 ml of N,N-dimethylformamide. After stirringfor 1 hour under nitrogen, the mixture was cooled to 5 C and 2.2 g of1-iodooctadecane were added. The mixture was allowed to warm to 22 C andstirred for 16 hours, then heated to 40 C for 2 hours. After quenchingwith 25 ml water and cooling to 22 C, the product was filtered andwashed with water. The product was dissolved in 25 ml hot ethanol with100 mg activated carbon, stirred for 30 minutes and filtered throughcelite. After adding 25 ml water and cooling to 5 C, the product wasfiltered, washed with water and dried leaving 2.1 g light yellow solid.

Hgx=N-Phenyl-N-pyridin-2-ylpyridin-2-amine

To a flask were added 0.5 g aniline, 2.1 g 2-bromopyridine, 1.3 g sodiumtert-butoxide, 0.15 g 1,1′-bis(diphenylphosphino)ferrocene and 50 mltoluene. The mixture was purged thoroughly with nitrogen and 0.12 g oftris(dibenzylideneacetone)d2-propanollladium(0) was added and themixture was heated to 80 C under nitrogen for 48 hours. After cooling to22 C most of the solvent was removed and the mixture was taken up in 100ml ethyl acetate and filtered. Following solvent removal, the productwas purified by silica gel chromatography using 50% ethyl acetate inhexane resulting in 0.62 g of oil which crystallized on standing.

Hgz=N—Propyl-N-pyridin-2-ylpyridin-2-amine

To a flask were added 5.0 g 2,2′-dipyridiylamine, 4.9 g of pulverizedpotassium hydroxide and 45 ml of N,N-dimethylformamide. After stirringfor 1 hour under nitrogen, the mixture was cooled to 5 C and 5.0 g of1-iodopropane were added. The mixture was allowed to warm to 22 C andstirred for 5 hours. After quenching with 45 ml water, the product wasextracted with ether and washed twice with water. Following removal ofsolvent, the product was purified by silica gel chromatography using 40%ethyl acetate in hexane to give 4.8 g of nearly colorless oil.

Hha=6-Methyl-N-(6-methylpyridin-2-yl)-N-propylpyridin-2-amine

6-Methyl-N-(6-methylpyridin-2-yl)pyridin-2-amine

To a flask were added 0.76 g 6-methyl-2-aminopyridine, 1.0 g2-bromo-6-methylpyridine, 0.95 g sodium tert-butoxide, 0.16 g1,1′-bis(diphenylphosphino)ferrocene and 50 ml toluene. The mixture waspurged thoroughly with nitrogen and 0.14 g oftris(dibenzylideneacetone)d2-propanollladium (0) was added and themixture was heated to 80 C under nitrogen for 3 hours. After cooling to22 C and quenching with 50 ml water, the product was extracted twicewith ethyl acetate and washed twice with water. After filtration andsolvent removal, the product was dissolved in 50 ml tert-butyl methylether and extracted into 60 ml 1M hydrochloric acid. Methanol was addedand the mixture was heated to dissolve the solids and the organic layerwas removed. The aqueous layer was basified with 3M sodium hydroxidesolution, the product was extracted with tert-butyl methyl ether andwashed with water. Following removal of solvent, an oil was obtainedthat was carried directly into the next step.

6-Methyl-N-(6-methylpyridin-2-yl)-N-propylpyridin-2-amine

To a flask were added 1.0 g6-methyl-N-(6-methylpyridin-2-yl)pyridin-2-amine, 0.84 g of pulverizedpotassium hydroxide and 15 ml of N,N-dimethylformamide. After stirringfor 1 hour under nitrogen, the mixture was cooled to 5 C and 0.85 g of1-iodopropane were added. The mixture was allowed to warm to 22 C andstirred for 16 hours. After quenching with 15 ml water, the product wasextracted twice with diethyl ether and washed with water. Followingremoval of solvent, the product was purified by silica gelchromatography using 10% ethyl acetate in hexane to give 11.0 g of acolorless oil.

Hhb=N,N-Bis(pyridin-2-ylmethyl)propan-1-amine

To a flask were added 1.0 g di-(2-picolyl)amine, 0.85 g of pulverizedpotassium hydroxide and 15 ml of N,N-dimethylformamide. After stirringfor 1 hour under nitrogen, the mixture was cooled to 5 C and 1.7 g of1-iodopropane were added. The mixture was heated to 35 C and stirred for16 hours. After quenching with 30 ml water, the product was extractedwith ethyl acetate and washed twice with water. Following removal ofsolvent, the product was purified by silica gel chromatography usingethyl acetate to give 0.65 g of a yellow oil.

Hhc=1-Propyl-4-pyridin-4-ylpyridinium iodide

To a flask were added 1.0 g 4,4′-dipyridyl, 1.07 g 1-iodopropane and 5 gacetonitrile and the mixture was allowed to stand at 22 C for 2 months.The liquid was decanted away from the solid and the solid was dissolvedin 15 ml hot acetonitrile. After hot filtration, the solution was cooledto 5 C and filtered. After washing with acetonitrile, the product wasdried leaving 0.8 g red-orange solid.

Hhd=Phenoxathiin

Hhh=Poly(2-vinylpyridine)

Hhj=Potassium O,O-diethyl thiophosphate

Hhl=Quinaldine

Hhv=Sodium Iodide

Hif=Tetrabutylammonium 3,5-Bis(trifluoromethyl)phenoxide

To a flask were added 11.0 g 3,5-bis(trifluoromethyl)phenol, 1.8 g of a55-60% solution of tetrabutylammonium hydroxide in water and 10 ml2-propanol. After heating to 50 C under nitrogen for 1 hour, the solventwas removed and another 10 ml of 2-propanol were added and removed bydistillation under reduced pressure. An oil was obtained whichcrystallized on standing.

Hii=Tetrabutylammonium Bis(hydroxymethyl)phosphinate

To a flask were added 0.48 g bis(hydroxymethyl)phosphinic acid, 1.6 g ofa 55-60% solution of tetrabutylammonium hydroxide in water and 10 ml2-propanol. After heating to 50 C under nitrogen for 1 hour, the solventwas removed and another 10 ml of 2-propanol were added and removed bydistillation under reduced pressure. An oil was obtained.

Hij=Tetrabutylammonium Bromide

Hik=Tetrabutylammonium Chloride

Hil=Tetrabutylammonium Di(4-Methoxyphenyl)phosphinate

To a flask were added 2.0 g bis(4-methoxyphenyl)phosphinic acid, 3.0 gof a 55-60% solution of tetrabutylammonium hydroxide in water, 2.0 g ofwater and 18 ml 2-propanol. After heating to 50 C under nitrogen for 1hour, the solvent was removed and another 20 ml of 2-propanol were addedand removed by distillation under reduced pressure. A waxy solid wasobtained.

Him=Tetrabutylammonium Dibenzoylmethanate

To a flask were added 3.0 g dibenzoylmethane, 5.7 g of a 55-60% solutionof tetrabutylammonium hydroxide in water and 20 ml 2-propanol. Afterheating to 50 C under nitrogen for 1 hour, the solvent was removed andanother 20 ml of 2-propanol were added and removed by distillation underreduced pressure. After drying the product, a yellow solid was obtained.

Hin=Tetrabutylammonium Dimethylolpropionate

To a flask were added 3.0 g 2,2-bis(hydroxymethyl)propionic acid, 9.5 gof a 55-60% solution of tetrabutylammonium hydroxide in water and 40 ml2-propanol. After heating to 50 C under nitrogen for 1 hour, the solventwas removed and another 40 ml of 2-propanol were added and removed bydistillation under reduced pressure. After drying, a pale yellow oil wasobtained.

Hio=Tetrabutylammonium Dimethylphosphinate

To a flask were added 11.0 g dimethylphosphinic acid, 4.5 g of a 55-60%solution of tetrabutylammonium hydroxide in water and 20 ml 2-propanol.After heating to 50 C under nitrogen for 1 hour, the solvent was removedand another 20 ml of 2-propanol were added and removed by distillationunder reduced pressure. After drying, a yellow partially solidifiedproduct was obtained.

Hir=Tetrabutylammonium Iodide

Hit=Tetrabutylammonium Methylphenylphosphinate

To a flask were added 2.0 g methylphenylphosphinic acid, 5.4 g of a55-60% solution of tetrabutylammonium hydroxide in water and 25 ml2-propanol. After heating to 50 C under nitrogen for 1 hour, the solventwas removed and another 20 ml of 2-propanol were added and removed bydistillation under reduced pressure. After drying, an oil was obtained.

Hiu=Tetrabutylammonium Nitrate

Hja=Tetrabutylammonium Thiocyanate

Hjd=Tetrabutylphosphonium Bromide

Hje=Tetraethylammonium Chloride Monohydrate

Hjf=Tetraethylammonium Diphenylphosphinate

To a flask were added 1.0 g diphenylphosphinic acid, 3.2 g of a 20%solution of tetraethylammonium hydroxide in water and 20 ml 2-propanol.After heating to 50 C under nitrogen for 1 hour, the solvent was removedand another 20 ml of 2-propanol were added and removed by distillationunder reduced pressure. After drying, an oil was obtained.

Hjg=Tetraethylammonium Iodide

Hjr=Tris(4-fluorophenyl)phosphine

Hjs=Tris(4-methoxyphenyl)phosphine

Hjt=Tris(2-methylphenyl)phosphine

Hju=Tris(4-methylphenyl)phosphine

Hjx=Tributylphosphine oxide

Hjy=Tricyclohexylphosphine

Hka=Triethylphosphine sulfide

Hke=Triphenylphosphine

Hkf=Triphenylphosphine oxide

Hkh=Triphenylphosphite

Hna=Thiazolo[2,3-b]benzimidazole-3(2H)-one

Hnd=1,2,4-Triazolo[1,5-a]pyrimidine

Hnf=2-Mercaptobenzothiazole

Hng=Tribenzylphosphine

Hnh=Benzyl(diphenyl)phosphine

Hnm=N,N-Bis[(1-methyl-1H-benzimidazol-2-yl)methyl]butanamine

2-(Chloromethyl)-1-methyl-1H-benzimidazole

To a pressure reaction bottle was added 4 g N-methyl-2-nitroaniline,0.44 g 5% palladium on carbon, and 100 ml ethanol. The mixture washydrogenated at 22 C and 40 psi hydrogen for 2 hours. Followingfiltration through celite, and solvent removal, a dark red oil wasobtained. To this oil was added 3.7 g chloroacetic acid and 40 ml 5Mhydrochloric acid. After refluxing under nitrogen for 2.5 hours, themixture was cooled to 22 C, diluted with 200 ml water, and neutralizedwith solid sodium bicarbonate. The resulting solid was filtered, washedwith water and dried giving 3.7 g gray solid.

N,N-Bis[(1-methyl-1H-benzimidazol-2-yl)methyl]butanamine

To a flask were added 2.0 g 2-(chloromethyl)-1-methyl-1H-benzimidazoleand 40 ml N,N-dimethylformamide. 0.41 g Butylamine were added dropwisefollowed by dropwise addition of 1.2 g of triethylamine. The reactionmixture was heated to 50 C under nitrogen for 16 hours, and then cooledto 22 C. After dilution with 100 ml water, the solid was filtered andwashed with water. The wet cake was dissolved in 20 ml of hot ethanoland 15 ml water was added. After cooling to 5 C, the solid was filteredand washed with 33% ethanol. The wet cake was dissolved in 15 ml of hotethanol and 10 ml water was added. After cooling to 5 C, the solid wasfiltered and washed with 33% ethanol. The product was then purified bysilica gel chromatography using 5% methanol in ethyl acetate to 10%methanol in ethyl acetate giving 0.93 g of a white solid.

Hnr=2,2′-Methylenebis(1H-benzimidazole)

To a flask were added 5 g of 1,2-phenylene diamine, 2.4 g of malonicacid, and 20 g of polyphosphoric acid. The mixture was heated to 180 Cunder nitrogen for 4 hours, and then cooled to 150 C. After the additionof 40 ml of water, the mixture was cooled to 22 C and neutralized withaqueous ammonium hydroxide. The solid was filtered and washed withwater. After triturating the product in 200 ml of hot acetonitrile, themixture was cooled to 22 C, filtered, washed with acetonitrile, anddried resulting in 2.7 g of a gray solid.

Hns=Indazole

Hnt=N′-[2-(Diethylamino)ethyl]-N,N-diethylethane-1,2-diamine

Hnu=2,2′-(1,3-Phenylene)bis(1-methyl-1H-benzimidazole)

To a Pressure reaction bottle was added 2.5 g ofN-methyl-2-nitroaniline, 0.3 g 5% palladium on carbon, and 65 mlethanol. The mixture was purged with hydrogen and then hydrogenatedunder 40 psi hydrogen for 1 hour. The catalyst was filtered off on a bedof celite. The solvent was removed and to the resulting red oil wasadded 70 g of polyphosphoric acid and 1.4 g of isophthalic acid. Thereaction mixture was heated to 200 C under nitrogen for 3 hours, andthen cooled to 150 C. After dilution with 150 ml water, the mixture wasbasified with sodium hydroxide. The solid was filtered, washed withwater, and then dissolved in 40 ml of hot methanol with 140 mg ofactivated carbon. After filtration of the activated carbon, enough waterwas added to turn the solution cloudy, and the mixture was decanted awayfrom a dark oil. After cooling to 5 C, more water was added causing aprecipitate which was filtered and washed with water. The solid wasdissolved in 26 ml of 2-propanol, filtered hot, and 10 ml of water wereadded. After cooling to 10 C, the solid was filtered, washed with 50%2-propanol, and dried, resulting in 1.1 g of an off-white solid.

Hnv=3-Methylbenzothiazole-2-thione

Hnw=1-Methyl-1H-benzimidazol-2-thiol

Hof=N-(Pyridin-2-ylmethyl)pyridin-2-amine

To a flask were added 4.7 g of 2-aminopyridine, 5.35 g of2-pyridinecarboxaldehyde, and 75 ml toluene. The flask was equipped witha Dean-Stark trap and heated to reflux under nitrogen. After 16 hours,the toluene was removed and 100 ml ethanol were added followed by 2.1 gof sodium borohydride. The mixture was stirred at 22 C under nitrogenfor 1 hour, and then 50 ml of water were added slowly. Following removalof the ethanol, aqueous ammonium chloride was cautiously added resultingin gas evolution. The product was extracted twice with 50 ml ethylacetate and washed with 30 ml water. After solvent removal, the productwas purified by silica gel chromatography using 5% methanol in ethylacetate resulting in an orange oil.

Hog=2-Mercaptobenzimidazole

Hos=2-Benzylpyridine

Hou=N-Ethyl-N-(pyridin-2-ylmethyl)pyridin-2-amine

To a flask were added 2.5 g N-(pyridin-2-ylmethyl)pyridin-2-amine and 40ml N,N-dimethylformamide, and the mixture was cooled to 5 C. To thismixture was added 0.65 g of 60% sodium hydride in mineral oil in smallportions, and after stirring at 5-10 C for ten minutes, 2.2 g of diethylsulfate were added. The reaction mixture was heated to 45 C for 16hours, then cooled to 22 C and quenched with 40 ml water. The productwas extracted twice with 40 ml hexane and following removal of thesolvent, the product was purified by silica gel chromatography using agradient from 50% ethyl acetate, 49% hexane and 1% methanol to 60% ethylacetate, 39% hexane, and 1% methanol resulting in 1.4 g of a yellow oil.

Hoz=N-(2-Ethylphenyl)-N-pyridin-2-ylpyridin-2-amine

To a flask were added 4.0 g of 2-ethylaniline, 10.7 g of2-bromopyridine, 7.9 g of sodium tert-butoxide, and 165 ml toluene. Themixture was purged thoroughly with nitrogen and 205 mg of2,2′-bis(diphenylphosphino)-1,1′-binaphthalenehthalene and 74 mg ofpalladium acetate were added. The reaction mixture was heated to 75 Cfor 16 hours, and then cooled to 22 C. After quenching with 100 mlwater, the product was extracted with 100 ml ethyl acetate, and washedwith 50 ml water. Following solvent removal, the product was purified bysilica gel chromatography using a gradient from 25% ethyl acetate inhexane to 50% ethyl acetate in hexane, resulting in 7.5 g of a yellowsolid.

Hpg=2,6-Pyridinedicarboxamide

Hpj=2-(1H-Pyrazol-3-yl)phenol

Hpo=2-(1-Methyl-1H-benzimidazol-2-yl)phenol

To a Pressure reaction bottle was added 3.5 g ofN-methyl-2-nitroaniline, 0.25 g 5% palladium on carbon, and 70 mlethanol. The mixture was purged with hydrogen and then hydrogenatedunder 40 psi hydrogen for 1.5 hours. The catalyst was filtered off on abed of celite. The solvent was removed and to the resulting red oil wasadded 2.9 g of salicylic acid, and a solution of 8 g of phosphoruspentoxide in 80 g of methanesulfonic acid. The reaction mixture washeated to 100 C under nitrogen for 16 hours, and then cooled to 22 C.After dilution with 300 ml of cold water, the mixture was neutralizedwith sodium hydroxide. After extraction with ethyl acetate andfiltration, the solvent was removed leaving an oil which partiallycrystallized on standing. After dissolving the product in hot 2-propanoland filtering hot, the solution was cooled to 5 C, filtered, and washedwith 2-propanol. The product was purified by silica gel chromatographyusing a gradient from 80% ethyl acetate in hexane to straight ethylacetate, resulting in 1.5 g of a tan solid.

Hqn=2,2′-Propane-2,2-diylbis(1-pentyl-1H-benzimidazole)

2.8 g 2,2′-Propane-2,2-diylbis(1H-benzimidazole) was added to 60 ml ofN,N-dimethylformamide. 1.21 g Of a 60% sodium hydride dispersion inmineral oil was added in portions. 6.0 g Of 1-iodopentane was added andthe mixture was stirred under nitrogen. After 4 hours, the reaction wasquenched with 160 ml of water and then extracted with two 75 ml portionsof ethyl acetate/methanol (˜99:1, v/v). The combined organic layers werewashed twice with 75 ml of water. The cloudy organic layer was filtered.Following solvent removal to give a brown oil, the product was purifiedby silica gel chromatography increasing from 25% to 50% ethyl acetate inhexane by volume over the course of the elution. 3.46 g Of a yellow oilwas obtained.

Hra=2,2′-Methylenebis(1-benzyl-1H-benzimidazole)

To a flask were added 2.0 g 2,2′-methylenebis(1H-benzimidazole), 2.8 gpotassium carbonate, 100 ml N,N-dimethylformamide and the mixture wasstirred under nitrogen. 2.5 g benzyl chloride were added and the mixturewas heated to 70 C for 16 hours. Another 0.7 g benzyl chloride was addedand the reaction was heated to 70 C for another 20 hours. The reactionwas cooled to 22 C, quenched with 150 ml water and the product wasextracted with ethyl acetate and washed with water. Following removal ofsolvent, the product was recrystallized from 10 ml ethanol, then 10 mlacetonitrile with 1 ml of water. The product was filtered and driedresulting in 0.67 g tan solid.

Hrb=2,2′-Ethane-1,2-diylbis(1-benzyl-1H-benzimidazole)

To a flask were added 0.5 g 2,2′-ethane-1,2-diylbis(1H-benzimidazole),0.7 g potassium carbonate, 30 ml N,N-dimethylformamide and the mixturewas stirred under nitrogen. 0.6 g Benzyl chloride were added and themixture was heated to 60 C for 16 hours. Another 0.5 g benzyl chloridewere added and the reaction was heated to 70 C for another 20 hours andthen cooled to 22 C. The reaction was quenched with 30 ml water and theproduct was filtered and washed with water. The product was re-slurriedin 80 ml hot acetonitrile, cooled, filtered and dried resulting in 0.35g of a white solid.

Hrc=2,2′-Methylenebis(1,3-benzothiazole)

To a flask were added 50 g polyphosphoric acid. After heating to 70 Cunder nitrogen, a mixture of 3.13 g 2-aminothiophenol and 1.3 g malonicacid was added. The reaction mixture was heated to 135 C for 1 hour,then 145 C for 1 hour. After cooling to 70 C, the mixture was pouredinto 100 ml water. The slurry was cooled to 22 C, filtered and the solidwas washed with water. The solid was added to 50 ml ethanol and basifiedwith aqueous ammonium hydroxide. After cooling to 5 C, the solid wasfiltered and washed with water. The solid was dissolved in 14 ml hotethanol and 7 ml water was added and the solution was cooled to 5 C.Following filtration, the white solid was washed with 50% ethanol anddried, leaving 1.1 g.

Hrg=Tetrabutylammonium Diisobutyldithiophosphinate

To 40 ml of 2-propanol, 3.63 g diisobutyldithiophosphinic acid and 7.34g of 55-60% by weight tetrabutylammonium hydroxide in water were added.The mixture was stirred under nitrogen for one hour. The solvent wasremoved by distillation. To remove residual water, 2-propanol was twiceadded and subsequently removed by distillation. The liquid was cooled toless than 0 C for 16 hours. To the precipitates that formed, a smallamount of hexane was added to give a slurry. The slurry was filtered,washed with hexane, and dried under reduced pressure yielding 6.07 g ofa white solid.

Hri=N,N-Bis(pyridin-2-ylmethyl)pentan-1-amine

To 15 ml of N,N-dimethylformamide, 0.85 g potassium hydroxide, 1.0 gdi(2-picolyl)amine, and 0.99 g 1-iodopentane were successively added.The mixture was stirred under nitrogen at 35 C for 2.5 hours before anadditional 0.99 g 1-iodopentane were added. The mixture was then stirredfor 16 hrs at 35 C under nitrogen. The reaction was quenched with 90 mlof water and extracted with two 50 ml portions of ethyl acetate. Thecombined organic layers were washed with two 25 ml portions of water,dried over anhydrous magnesium sulfate, and filtered. Following solventremoval, the orange oil obtained was purified by silica gelchromatography using a methanol/ethyl acetate mixed solvent system thatwas ramped from 0% to 10% methanol by volume during the course of theelution. An orange oil (0.98 g) was obtained.

Hrk=1-(Chloromethyl)-4-aza-1-azoniabicyclo[2.2.2]octane bromide

20 ml Of acetone, 4.0 g of 1,4-diazabicyclo[2.2.2]octane, and 20 ml ofbromochloromethane, were added to a flask, capped, and stirred at roomtemperature. Within 45 minutes white precipitate had formed. After 3.5hours the mixture was cooled to 0-5 C, filtered, washed with three 10 mlportions of cold acetone, and dried under reduced pressure overnight.2.31 g Of a white solid was obtained.

Hrl=N-Methylpyridin-2-amine

Hrm=Tetraphenylphosphonium Iodide

Hry=1-Ethyl-N-methyl-N-pyridin-2-yl-1H-benzimidazol-2-amine

2-Bromo-1H-benzimidazole

To a flask were added 24 ml 48% hydrobromic acid and 120 ml methanol.The mixture was cooled to 5 C and 10 g 2-mercaptobenzimidazole wasadded. Maintaining a temperature of less than 10 C, 41.5 g of brominewere added in small portions. The mixture was allowed to warm to 22 C,and stirred for 16 hours under nitrogen. After cooling to 5 C, the solidwas filtered and then added to 50 ml methanol containing 20 ml aqueousammonium hydroxide. The pH was adjusted to 6.5 with acetic acid, and themixture was cooled to 5 C. The product was filtered and washed withwater, and dried. A second crop was obtained by cooling the filtrateswhich was filtered, washed with water and dried. The combined cropsresulted in 9.05 g of a solid.

2-Bromo-1-ethyl-1H-benzimidazole

To a flask were added 4 g 2-bromo-1H-benzimidazole and 60 mltetrahydrofuran, and the mixture was cooled to 10 C. To this mixture wasadded 1.2 g of 60% sodium hydride in mineral oil in small portions, andafter stirring at 10 C for ten minutes, 4.7 g of diethyl sulfate wereadded. The reaction mixture was heated to 40 C for several hours, thencooled to 22 C and quenched with 100 ml water. The product was extractedtwice with 50 ml ethyl acetate and following removal of the solvent, theproduct was purified by silica gel chromatography using a gradient from100% hexane to 25% ethyl acetate in hexane. An oil was obtained thatcrystallized on standing which was dried resulting in 4.2 g of a whitesolid.

1-Ethyl-N-methyl-N-pyridin-2-yl-1H-benzimidazol-2-amine

To a flask were added 11.0 g of 2-bromo-1-ethyl-1H-benzimidazole, 0.482-(methylamino)pyridine, 0.64 g of sodium tert-butoxide, and 25 mltoluene. The mixture was purged thoroughly with nitrogen and 250 mg of2,2′-bis(diphenylphosphino)-1,1′-binaphthalene and 64 mg of palladiumacetate were added. The reaction mixture was heated to 90 C for 16hours, and then cooled to 22 C. After quenching with 50 ml water, theproduct was extracted with 20 ml ethyl acetate. The product wasextracted with 30 ml of 1M hydrochloric acid, and then basified with 3Msodium hydroxide. Following extraction with 20 ml ethyl acetate, theproduct was purified by silica gel chromatography using a gradient from40% ethyl acetate in hexane to 70% ethyl acetate in hexane, resulting in0.6 g of a yellow oil which crystallized on standing. The product wasrecrystallized from a mixture of 5 ml hexane with 1.5 ml 2-propanol.After filtration and drying of the product, a 0.44 g of a yellow solidwas obtained.

Hrz=2,2-Dimethyl-N,N-dipyridin-2-ylpropanamide

To a flask were added 2.0 g of 2,2′-dipyridylamine and 35 ml ofacetonitrile. The solution was stirred under nitrogen and cooled to 5 C,when 1.5 g of triethylamine were added, followed by 1.5 g oftrimethylacetyl chloride and the mixture was allowed to warm to 22 C.After 1 hour, 50 ml of water were added and the acetonitrile wasremoved. The product was extracted with ethyl acetate and washed withwater. Following solvent removal, the product was purified by silica gelchromatography using 50% ethyl acetate in hexane, resulting in 1.8 g ofan oil that solidified on standing.

Hsc=2,2-Dimethyl-N-(6-methylpyridin-2-yl)-N-pyridin-2-ylpropanamide

To a flask were added 1.06 g of di-(2-picolyl)amine and 20 ml ofacetonitrile. The solution was stirred under nitrogen, when 0.7 g oftriethylamine were added, followed by 1.5 g of trimethylacetyl chloride.After 1 hour, 20 ml of water were added and the acetonitrile wasremoved. The product was extracted with ethyl acetate and washed withwater. Following solvent removal, the product was recrystallized bydissolving in 6 ml hot hexane with 0.5 ml 2-propanol. Another 2 mlhexane were added and the mixture was cooled to 5 C, filtered, washedwith hexane and dried, resulting in 1.3 g of an off-white solid.

Hss=6-methyl-N-phenyl-N-pyridin-2-ylpyridin-2-amine

6-Methyl-N-phenylpyridin-2-amine

To a flask were added 2.2 g of 2-amino-6-methylpyridine, 3.1 g ofbromobenzene, 2.7 g of sodium tert-butoxide, and 50 ml toluene. Themixture was purged thoroughly with nitrogen and 62 mg of2,2′-bis(diphenylphosphino)-1,1′-binaphthalenehthalene and 22 mg ofpalladium acetate were added. The reaction mixture was heated to 100 Cfor 16 hours, and then cooled to 22 C. After quenching with 50 ml water,the product was extracted with 20 ml ethyl acetate, and washed with 15ml water. The product was extracted with 50 ml of 1M hydrochloric acid,and then basified with aqueous ammonium hydroxide. Following extractionwith 20 ml ethyl acetate, the product was purified by silica gelchromatography using a gradient from 10% ethyl acetate in hexane to 15%ethyl acetate in hexane, resulting in 1.3 g of a yellow-orange oil.

6-Methyl-N-phenyl-N-pyridin-2-ylpyridin-2-amine

To a flask were added 18.4 g of 6-methyl-N-phenylpyridin-2-amine, 15.8 gof 2-bromopyridine, 11.5 g of sodium tert-butoxide, and 250 ml toluene.The mixture was purged thoroughly with nitrogen and 270 mg of1,1′-bis(diphenylphosphino)ferrocene and 10 mg of palladium acetate wereadded. The reaction mixture was heated to 90 C for 6 hours, and thencooled to 22 C. After quenching with 100 ml water, the product wasextracted with 75 ml ethyl acetate. The product was extracted with 50 mlof 1M hydrochloric acid, and then basified with sodium hydroxide. Themixture was cooled to 5 C, and the crude product was filtered and washedwith water. The product was dissolved in 100 ml hot 2-propanol andtreated with 0.4 g activated carbon. After hot filtration through a bedof celite, 150 ml of water was added slowly and the mixture was seededto induce crystallization. After cooling to 5 C, the product wasfiltered and washed with 50 ml of 33% 2-propanol in water. The productwas dried resulting in 21 g of a light tan solid.

Hst=N-Pyridin-2-yl-N-(pyridin-2-ylmethyl)pyridin-2-amine

To a flask were added 5.2 g pulverized potassium hydroxide and 35 mldimethylsulfoxide. After adding 3.4 g 2,2′-dipyridylamine, the mixturewas stirred under nitrogen for 45 minutes, when 3.3 g2-(chloromethyl)pyridine hydrochloride was added. After stirring for 1hour, 100 ml of water was added and the product was extracted with 60 mlof 50% ethyl acetate, 50% hexane. The organic layer was washed with 30ml water and the solvent was removed. The residue was added to 5 ml hotethanol, and 20 ml of water was added. After cooling to 5 C, the solidwas filtered and washed with water. The product was dissolved in 20 mlhot ethanol and treated with 150 mg activated carbon. After hotfiltration through celite, 40 ml of water were added and the mixture wascooled to 5 C. The product was filtered, washed with 20 ml 20% ethanolin water, and dried resulting in 2.9 g of an off-white solid.

Hsz=N-[(6-Methylpyridin-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine

To a flask were added 0.6 g pulverized potassium hydroxide and 15 mldimethylsulfoxide. After adding 1.4 g of 2,2′-dipyridylamine, themixture was stirred under nitrogen for 45 minutes, when 1.5 g6-methyl-2-(bromomethyl)pyridine was added. After stirring for 1 hour,35 ml of water was added and the product was extracted with 60 ml of 50%ethyl acetate, 50% hexane. The organic layer was washed with 30 ml waterand the solvent was removed. The residue was purified by silica gelchromatography using 48% ethyl acetate, 48% hexane, and 4% methanolresulting in 2.0 g of an oil.

Htd=2-Pyridin-2-ylethanamine

Htk=N-Methyl-N-[(1-methyl-1H-benzimidazol-2-yl)methyl]pyridin-2-amine

To a flask were added 0.6 g 2-(methylamino)pyridine and 20 mltetrahydrofuran, and the mixture was cooled to 5 C. To this mixture wereadded 0.26 g of 60% sodium hydride in mineral oil in small portions, andafter stirring at 5-10 C for ten minutes, 1.0 g of2-(chloromethyl)-1-methyl-1H-benzimidazole was added. The reactionmixture was heated to 45 C for 16 hours, then cooled to 22 C andquenched with 40 ml water. The product was extracted with 40 ml ethylacetate and following removal of the solvent, the product was purifiedby silica gel chromatography using 63% ethyl acetate, 25% hexane and 12%methanol resulting in 0.55 g of a yellow solid.

Htm=N,N′,N′,2,2-Hexamethylpropane-1,3-diamine

Hto=6-Methyl-N-pyridin-2-ylpyridin-2-amine

To a flask were added 3.2 g of 2-amino-6-methylpyridine, 4.9 g of2-bromopyridine, 3.5 g of sodium tert-butoxide, and 120 ml toluene. Themixture was purged thoroughly with nitrogen and 83 mg of1,1′-bis(diphenylphosphino)ferrocene and 34 mg of palladium acetate wereadded. The reaction mixture was heated to 65 C for 3 hours, to 75 C for2 hours, and then cooled to 22 C. After quenching with 75 ml of water,the product was extracted with 75 ml ethyl acetate. The product wasextracted with 50 ml of 1M hydrochloric acid, and washed with 30 ml ofethyl acetate. After basifying with 3M sodium hydroxide, the product wasextracted with 75 ml of ethyl acetate and washed with 30 ml of water.Following solvent removal, the product was purified by silica gelchromatography using 38% ethyl acetate, 50% hexane, and 12% methanolresulting in an orange oil.

Htp=P,P-Diphenyl-N,N-dipyridin-2-ylphosphinous amide

Htq=N-[(1-Methyl-1H-benzimidazol-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine

To a flask were added 1.1 g of 2,2′-dipyridylamine and 25 ml ofN,N-dimethylformamide. To this mixture were added 0.32 g of 60% sodiumhydride in mineral oil in small portions, and after stirring at 10 C forten minutes, 1.2 g of 2-(chloromethyl)-1-methyl-1H-benzimidazole in 5 mlof N,N-dimethylformamide were added. The reaction mixture was stirred at22 C for several hours, and then quenched with 40 ml water. The productwas extracted with 50 ml ethyl acetate, and then extracted with 30 ml of1M hydrochloric acid, and basified with 3M sodium hydroxide. Followingextraction with 20 ml ethyl acetate, the product was purified by silicagel chromatography using 33% ethyl acetate, 62% hexane, and 5% methanol,resulting in an oil which crystallized on standing. After drying, 0.6 gof a yellow solid remained.

Hui=6-Methyl-N-[(6-methylpyridin-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine

2-(Bromomethyl)-6-methylpyridine

To a flask containing a mixture of 15 ml of 48% hydrobromic acid and 11ml of sulfuric acid was added 5 g of 6-methyl-2-pyridinemethanoldropwise under nitrogen. The mixture was heated to 90 C for 4 hours, andpoured into 25 ml of water. After neutralization with sodium carbonate,the product was extracted with 100 ml ethyl acetate and washed with 30ml of water. Following solvent removal, the product was purified bysilica gel chromatography using 25% ethyl acetate in hexane, resultingin 6.3 g of a pink oil which solidified on storage at −5 C.

6-Methyl-N-[(6-methylpyridin-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine

To a flask were added 1.7 g pulverized potassium hydroxide and 15 mldimethylsulfoxide. After adding 1.5 g 6-methyl-2,2′-dipyridylamine, themixture was stirred under nitrogen for 45 minutes, when 1.6 g2-(bromomethyl)-6-methylpyridine was added. After stirring for 1 hour,35 ml of water was added and the product was extracted with 60 ml of 50%ethyl acetate, 50% hexane. The organic layer was washed with 30 ml waterand the solvent was removed. The residue was purified by silica gelchromatography using 48% ethyl acetate, 48% hexane, and 4% methanolresulting in 1.95 g of a yellow oil.

Huj=N-(6-Methylpyridin-2-ylmethyl)pyridin-2-amine

To a flask were added 1.9 g of 2-aminopyridine, 2.4 g of6-methyl-2-pyridinecarboxaldehyde and 45 ml toluene. The flask wasequipped with a Dean-Stark trap and heated to reflux under nitrogen.After 16 hours, the toluene was removed and 40 ml ethanol were addedfollowed by 0.83 g of sodium borohydride. The mixture was stirred at 22C under nitrogen for 1 hour, and then 30 ml of water were added slowly.Following removal of the ethanol, 60 ml 1M hydrochloric acid was addedcautiously, and the aqueous layer was washed with 20 ml ethyl acetate.After basifying with aqueous ammonium hydroxide, the product wasextracted with 50 ml ethyl acetate and the solvent was removed. Theproduct was purified by silica gel chromatography using 74% ethylacetate, 24% hexane, and 2% methanol resulting in 1.5 g of a yellow oilthat solidified on standing.

Hur=Potassium hydrotris(3,5-dimethylpyrazol-1-yl)borate

Hvm=6-Methyl-N,N-dipyridin-2-ylpyridin-2-amine

To a flask were added 3.7 g of 6-methyl-N-pyridin-2-ylpyridin-2-amine,9.4 g of 2-bromopyridine, 2.0 g of sodium carbonate, 0.05 g of copperbronze, 0.01 g of potassium bromide, and 5 ml of mesytylene. Afterstirring under nitrogen at 160 C for 10 hours, the mixture was cooled to22 C, and 35 ml of water was added and the product was extracted with 75ml ethyl acetate. After washing twice with 30 ml of water, the solventwas removed, and the product was purified by silica gel chromatographyusing 75% ethyl acetate, 25% hexane, and 0.01% triethylamine resultingin 3.2 g of a yellow oil.

Hvn=2-Methyl-N-(6-methylpyridin-2-yl)-N-pyridin-2-ylquinolin-8-amine

2-Methylquinolin-8-amine

To a Pressure reaction bottle was added 5.0 g of 8-nitroquinaldine, 0.5g 5% palladium on carbon, and 150 ml ethanol. The mixture was purgedwith hydrogen and then hydrogenated under 40 psi hydrogen for 16 hours.The catalyst was filtered off on a bed of celite. The solvent wasremoved, resulting in 4.2 g of a dark oil.

2-Methyl-N-(6-methylpyridin-2-yl)quinolin-8-amine

To a flask were added 4.2 g of 2-methylquinolin-8-amine, 4.6 g of6-methyl-2-bromopyridine, 3.3 g of sodium tert-butoxide, and 75 mltoluene. The mixture was purged thoroughly with nitrogen and 44 mg of1,1′-bis(diphenylphosphino)ferrocene and 18 mg of palladium acetate wereadded. The reaction mixture was heated to 80 C for 16 hours, and thencooled to 22 C. After quenching with 100 ml of water, the product wasextracted with 75 ml ethyl acetate. The product was extracted with 120ml of 1M hydrochloric acid, and then basified with 3M sodium hydroxide.Following extraction with 75 ml of ethyl acetate and washing with 30 mlof water, the solvent was removed. The product was purified bydissolving in a hot mixture of 20 ml of 2-propanol and 5 ml of water,and after cooling to 5 C, the product was filtered, washed with 50%2-propanol, and dried, resulting in 4.5 g of a tan solid.

2-Methyl-N-(6-methylpyridin-2-yl)-N-pyridin-2-ylquinolin-8-amine

To a flask were added 2.5 g of2-methyl-N-(6-methylpyridin-2-yl)quinolin-8-amine, 4.7 g of2-bromopyridine, 1.6 g of sodium carbonate, 51 mg of copper bronze, 5 mgof potassium bromide, and 3 ml of mesytylene. After stirring undernitrogen at 160 C for 16 hours, the mixture was cooled to 22 C, and 35ml of water was added and the product was extracted with 50 ml ethylacetate. After washing twice with 20 ml of water, the solvent wasremoved, and the product was purified by silica gel chromatography using50% ethyl acetate, 50% hexane, and 0.1% triethylamine resulting in 3.0 gof a light yellow oil.

Hvo=6-Methyl-N-(6-methylpyridin-2-yl)-N-pyridin-2-ylpyridin-2-amine

6-Methyl-N-(6-methylpyridin-2-yl)pyridin-2-amine

To a flask were added 3.1 g of 2-amino-6-methylpyridine, 5.0 g of2-bromo-6-methylpyridine, 3.6 g of sodium tert-butoxide, and 150 mltoluene. The mixture was purged thoroughly with nitrogen and 160 mg of1,1′-bis(diphenylphosphino)ferrocene and 65 mg of palladium acetate wereadded. The reaction mixture was heated to 80 C for 3 hours, and thencooled to 22 C. After quenching with 100 ml of water, the product wasextracted with 75 ml ethyl acetate. The product was extracted with 75 mlof 1M hydrochloric acid, and then basified with 3M sodium hydroxide.Following extraction with 75 ml of ethyl acetate and washing with 30 mlof water, the solvent was removed. The product was purified bydissolving in a minimum amount of hot 2-propanol, and after cooling to 5C, the product was filtered, washed with cold 2-propanol, and dried,resulting in 3.3 g of a tan solid.

6-Methyl-N-(6-methylpyridin-2-yl)-N-pyridin-2-ylpyridin-2-amine

To a flask were added 2.0 g of6-methyl-N-(6-methylpyridin-2-yl)pyridin-2-amine, 4.7 g of2-bromopyridine, 1.6 g of sodium carbonate, 51 mg of copper bronze, 5 mgof potassium bromide, and 3 ml of mesytylene. After stirring undernitrogen at 160 C for 16 hours, the mixture was cooled to 22 C, and 35ml of water was added and the product was extracted with 50 ml ethylacetate. After washing twice with 20 ml of water, the solvent wasremoved, and the product was purified by silica gel chromatography using60% ethyl acetate, 40% hexane, and 0.1% triethylamine resulting in 2.2 gof a yellow oil.

Hvw=2,2′-(1,2-Phenylene)bis(1-pentyl-1H-benzimidazole)

To a flask were added 1.5 g of 2,2′-(1,2-phenylene)bis(1H-benzimidazole)and 30 ml of N,N-dimethylformamide, and the mixture was cooled to 5 C.To this mixture was added 0.48 g of 60% sodium hydride in mineral oil insmall portions, and after stirring at 5-10 C for 30 minutes, 2.4 g of1-1-iodopentane were added. The reaction mixture was warmed to 22 C forand stirred for 16 hours, then quenched with 50 ml water. The productwas extracted with 40 ml ethyl acetate and following removal of thesolvent, the product was purified by silica gel chromatography using 25%ethyl acetate, 75% hexane and 0.1% triethylamine resulting in 2.1 g of ayellow solid.

Hwa=3-Methylpyridazine

Hwc=1-Butyl-1H-imidazole

Hwq=Hexamethylphosphoramide

1. A thermochromic system comprising: a) Ni(II); b) a first ligand whichforms a LεMLC with Ni(II); c) a second ligand which forms a HεMLC withNi(II); and d) a polymer wherein the system is in the form of a solid orsemi-solid layer and the system exhibits a reversible net increase inlight energy absorbance in the 400 nm to 1400 nm range as thetemperature of the system is increased.
 2. The thermochromic system ofclaim 1, wherein the system further comprises at least one of a UVabsorber, a hindered amine light stabilizer, a thermal stabilizer, and aplasticizer.
 3. The thermochromic system of claim 1, wherein the systemincludes a plasticizer wherein the plasticizer is cation with thefollowing structure:

wherein X is N or P and wherein R₁, R₂, R₃ and R₄ are independentlyselected from the group consisting of straight, branched, substituted orunsubstituted alkyl; substituted or unsubstituted aryl, substituted orunsubstituted aralkyl and combinations thereof.
 4. The thermochromicsystem of claim 1, wherein the haze level in the solid or semi-solidlayer is below 5%.
 5. The thermochromic system of claim 4, wherein thehaze level in the solid layer is below 10% after 500 hours of exposureto 0.55 watts per square meter at 340 nm from a xenon arc lamp in achamber with a black panel temperature of 80 C.
 6. The thermochromicsystem of claim 1, wherein the first ligand comprises a LεL selectedfrom the group consisting of the polymer, diols, triols, polyols andcombinations thereof.
 7. The thermochromic system of claim 1, whereinthe first ligand comprises a hydroxyl group and the ratio of theconcentration of the second ligand to the concentration of the Ni(II)([HεL_(T)]/[Ni(II)_(T)]) is greater than four.
 8. The thermochromicsystem of claim 1, wherein the absorption increase is due to theformation of a HεMLC of Ni(II) with an absorption peak with a λ_(max)between 400 nm and 640 nm.
 9. The thermochromic system of claim 1,wherein the total concentration of Ni(II) is between about 0.04 molesand 0.4 moles of Ni(II) per kilogram of polymer.
 10. A thermochromicsystem which comprises Ni(II) in a polymer wherein the system has areversible, net increase in its ability to absorb in the 400 nm to 1400nm range due to a change in coordination of the Ni(II) in a coordinationcompound of Ni(II) as the temperature of the system is increased. 11.The thermochromic system of claim 10 wherein the system furthercomprises a diol, a triol or polyol and the coordination compoundcomprises a ligand which coordinates to the Ni(II) through a nitrogen, aphosphorous or a sulfur.
 12. The thermochromic system of claim 10,wherein the absorbance of the system at 25° C. is less than about 0.3throughout in the 400 nm to 1400 nm range.
 13. The thermochromic systemof claim 10 wherein the system further comprises a phosphine ligand andthe reversible, net increase in the ability of the system to absorblight energy in the visible and NIR range as the temperature of thesystem is increased is due to a reversible increase in concentration ofa coordination compound between the phosphine ligand and the Ni(II) asthe temperature is increased.
 14. The thermochromic system of claim 10wherein the system further comprises iodide ions and the reversible, netincrease in the ability of the system to absorb light energy in thevisible and NIR range as the temperature of the system is increased isdue to a reversible increase in concentration of a coordination compoundbetween the iodide ions and the Ni(II) as the temperature is increased.15. The thermochromic system of claim 14 wherein the thermochromicsystem further comprises a phosphine compound at a concentration belowthe concentration of the Ni(II) ions.
 16. The thermochromic system ofclaim 10 wherein the thermochromic system further comprises a phosphineligand and iodide ions and the reversible, net increase in the abilityof the system to absorb light energy in the 400 nm to 1400 nm range asthe temperature of the system is increased is due to a reversibleincrease in concentration of a coordination compound between Ni(II) andboth iodide and the phosphine ligand as the temperature is increased.17. A thermochromic system comprising: a) Ni(II) b) a first ligandcomprising a pseudohalide or a halide, wherein the halide is selectedfrom the group consisting of Cl—, Br—, I— and combinations thereof, andc) a second ligand comprising a nitrogen-containing ligand, aphosphorous-containing ligand or a sulfur-containing ligand; wherein thesystem has a reversible, net increase in its ability to absorb lightenergy in the 400 nm to 1400 nm range as the temperature of the systemis increased.
 18. The thermochromic system of claim 17 wherein the netincrease in absorbance is due to an increase in concentration of acoordination compound between Ni(II), the first ligand and the secondligand.
 19. A thermochromic system comprising: a) Co(II) b) a firstligand comprising a pseudohalide or a halide, wherein the halide isselected from the group consisting of Cl—, Br—, I— and combinationsthereof, and c) a second ligand comprising an oxygen containing ligand,a phosphorous-containing ligand or a sulfur-containing ligand, whereinthe second ligand is capable of coordinating to a transition metal ionthrough oxygen, phosphorus or sulfur; wherein the system has areversible, net increase in its ability to absorb light energy in the400 nm to 1400 nm range as the temperature of the system is increased.20. A thermochromic system comprising: a) a HεMLC of Co(II); b) a firstligand selected from the group consisting of diols, triols, polyols andcombinations thereof, and c) a second ligand which coordinates to theCo(II) through an oxygen atom or an oxygen anion; wherein the systemexhibits a reversible increase in concentration due to a change incoordination as the temperature is increased.
 21. The thermochromicsystem of claim 20, wherein the second ligand comprises a phosphinateanion.
 22. The thermochromic system of claim 21, wherein the phosphinateanion is selected from the group consisting of anions of the followingstructure and mixtures thereof:

wherein R and R′ are independently selected from the group consisting ofoptionally substituted, straight and branched chain alkyl, aralkyl,aryl, substituted aryl and combinations thereof.
 23. The thermochromicsystem of claim 21, wherein the phosphinate anions are provided as saltsof alkali metal cations, quaternary ammonium cations or quaternaryphosphonium cations.
 24. The thermochromic system of claim 21, whereinthe phosphinate anion is selected from the group consisting ofbis(hydroxymethyl)phosphinate, bis(4-Methoxyphenyl)phosphinate,methylphenylphosphinate, diphenylphosphinate, dimethylphosphinate andmixtures thereof.
 25. The thermochromic system of claim 20, wherein thesecond ligand is part of a carboxylate anion.
 26. The thermochromicsystem of claim 25, wherein the carboxylate anion is selected from thegroup consisting of acetate, trifluoroacetate, benzoate2-methoxybenzoate, salicylate malonate, succinate, phthalate andmixtures thereof.
 27. The thermochromic system of claim 20, wherein thesecond ligand is part of a phosphine oxide.
 28. The thermochromic systemof claim 27, wherein the phosphine oxide is selected from the groupconsisting of hexamethylphosphoramide, tributylphosphine oxide,triphenylphosphine oxide and mixtures thereof.
 29. The thermochromicsystem of claim 20, wherein the second ligand is part of a nitrateanion, a pyridine-N-oxide or a phenolate anion.
 30. The thermochromicsystem of claim 20, wherein the HεMLC of Co(II) comprises a heterolepticcomplex comprising a halide anion.
 31. A thermochromic system comprisinga) Co(II); b) Iodide; and c) either a first ligand, a second ligand orboth wherein the first ligand is selected from the group consisting of adiol, a triol, a polyol, and mixtures thereof and the second ligandcomprises one or more phosphine compounds, wherein the system exhibits areversible, net increase in its ability to absorb light energy in the400 nm to 1400 nm range as the temperature of the system is increased.32. The thermochromic system of claim 31, wherein the system comprisesthe second ligand, which comprises a phosphine compound having thestructure:

wherein R₁, R₂ and R₃ are independently selected from the groupconsisting of optionally substituted alkyl, optionally substitutedcycloalkyl, optionally substituted aryl and combinations thereof.
 33. Athermochromic system comprising Co(II) ions and a phosphine compoundwherein the system exhibits a reversible, net increase in the system'sability to absorb energy in the 400 nm to 1400 nm of the electromagneticradiation from the sun, as the temperature of the system is increased,due to a reversible increase in concentration of a coordination compoundof the phosphine compound with Co(II) ions.
 34. The thermochromic systemof claim 33 wherein the system further comprises iodide ions, and thereversible, net increase in the system's ability to absorb energy in the400 nm to 1400 nm of the electromagnetic radiation from the sun, as thetemperature of the system is increased is due to a reversible increasein concentration of a heteroleptic coordination compound between thephosphine compound and iodide ions with Co(II) ions.
 35. A thermochromicsystem comprising: a) a polymer; b) Co(II) ions; c) a first ligand thatforms a HεMLC with Co(II); and d) a second ligand that forms a LεMLCwith Co(II), wherein the second ligand is represented by the followingstructure:

wherein R is selected from the group consisting of H, alkyl, substitutedalkyl, branched alkyl, aralkyl, aryl, amino, substituted amino, nitroand combinations thereof.
 36. The thermochromic system of claim 35,wherein the second ligand is selected from the group consisting oftrimetholmethane, trimethylolethane, trimethylpropane,trimethylolbutane, pentaerythritol, di-pentaerythritol,trimethylolnitromethane, trimethylolaminomethane and mixtures thereof.37. The thermochromic system of claim 35, wherein the first ligand isselected from the group consisting of chloride, bromide, iodide andmixtures thereof.
 38. A thermochromic system comprising a polymer layerand: a) a transition metal ion; b) a first ligand capable of forming aHεMLC with the transition metal ion; and c) a second ligand representedby the following structure:

wherein R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from thegroup consisting of straight, branched, substituted or unsubstitutedalkyl, substituted or unsubstituted aryl, substituted or unsubstitutedaralkyl and combinations thereof, provided that optionally anycombination of two or more of R₁, R₂, R₃, R₄, R₅ and/or R₆ may be joinedtogether to form one or more optionally substituted ring systems. 39.The thermochromic system of claim 38 wherein the second ligand is a diolligand selected from the group consisting of 1,3-Cyclohexanediol;1,1-Bis(hydroxymethyl)cyclopropane; 2,2-Bis(hydroxymethyl)propionicacid; 2,2-Dibutyl-1,3-propanediol; 2,2-Diethyl-1,3-propanediol;2,2,4-Trimethyl-1,3-pentanediol; 2,4-Dimethyl-2,4-pentanediol;2,4-Pentanediol; 2-Bromo-2-nitro-1,3-propanediol; Serinol;2-Butyl-2-Ethyl-1,3-propanediol; 2-Ethyl-1,3-hexanediol;2-Methyl-1,3-propanediol; 2-Methyl-2,4-pentanediol;2-Methyl-2-propyl-1,3-propanediol; 2-Methylenepropane-1,3-diol;2-Phenyl-1,3-propanediol; Cyclohex-3-ene-1,1-diyldimethanol;3-Methyl-1,3-butanediol; 3-Methyl-2,4-heptanediol;[2-(2-phenylethyl)-1,3-dioxane-5,5-diyl]dimethanol; Neopentyl Glycol;Trimethylolpropane allyl ether and mixtures thereof.
 40. Thethermochromic system of claim 38 wherein the transition metal ion isselected from the group consisting of Fe(II), Co(II), Ni(II), Cu(II) andmixtures thereof.
 41. The thermochromic system of claim 40 wherein thefirst ligand is iodide.
 42. A thermochromic system which comprises apolymer layer which comprises: a) a transition metal ion; b) a firstligand capable of forming a HεMLC with the transition metal ion; and c)a second ligand with the follow structure:

wherein R is selected from the group consisting of straight, branched,substituted or unsubstituted alkyl; substituted or unsubstituted aryl;substituted or unsubstituted aralkyl; a nitro group, a substituted orunsubstituted amino group and combinations thereof.
 43. Thethermochromic system of claim 42 wherein the second ligand is selectedfrom the group consisting of2,2′-(propane-1,3-diyldiimino)bis[2-(hydroxymethyl)propane-1,3-diol];2-[bis(2-hydroxyethyl)amino]-2-(hydroxymethyl)propane-1,3-diol;Dipentaerythritol; Pentaerythritol;2-(bromomethyl)-2-(hydroxymethyl)propane-1,3-diol;2-(hydroxymethyl)-2-propylpropane-1,3-diol;2-(hydroxymethyl)-2-methylpropane-1,3-diol;2-(hydroxymethyl)propane-1,3-diol;2-(hydroxymethyl)-2-nitropropane-1,3-diol; Trimethylolpropane;2-amino-2-(hydroxymethyl)propane-1,3-diol and mixtures thereof.
 44. Athermochromic system comprising a polymer layer and a) a transitionmetal ion; b) a first ligand capable of forming a HεMLC with thetransition metal ion; and c) a second ligand capable of forming a LεMLCwherein the second ligand is selected from the group consisting ofDi(Trimethylolpropane); L-Fucose; meso-Erythritol;N-propyl-N-pyridin-2-ylpyridin-2-amine; Poly(vinylbutyral);Poly(vinylpyrrolidone); Tetrahydrofurfuryl alcohol;Tetrahydropyran-2-methanol; Triethanolamine; 1,2,4-Butanetriol;1,2-phenylenedimethanol; 1,2-Hexanediol; 1,2-Propanediol;cis,cis-1,3,5-Cyclohexanetriol; 1,3,5-Pentanetriol;2,5-bis(hydroxymethyl)-1,4-dioxane-2,5-diol; 1,4-Butanediol;1,4-Cyclohexanediol; 18-Crown-6; 1-ethyl-1H-benzimidazole;2,3-Dimethyl-2,3-butanediol; 2-Phenyl-1,2-Propanediol;3-(Diethylamino)-1,2-propanediol;2-ethyl-2-(hydroxymethyl)butane-1,4-diol; 3,3-Dimethyl-1,2-butanediol;3-Hydroxypropionitrile; 3-Methyl-1,3,5-Pentanetriol;3-Phenoxy-1,2-Propanediol; 4-Hydroxy-4-methyl-2-pentanone;3-Phenyl-1-propanol; (5-methyl-1,3-dioxan-5-yl)methanol;Bis(methylsulfinyl)methane; Butyl sulfoxide; Diethylene glycol;Diethylformamide; Hexamethylphosphoramide; 3,3′-oxydipropane-1,2-diolDimethyl sulfoxide; Ethanol; Ethylene Glycol; Glycerol; Glycolic Acid;3-(2-methoxyphenoxy)propane-1,2-diol; Lithium Salicylate; LithiumTrifluoroacetate; N,N-Dimethylformamide; 1,1,3,3-Tetramethylurea;2,2-dimethylpropan-1-ol; Pentaethylene glycol; Pentaerythritolethoxylate; tetrahydrothiophene 1-oxide; Tributylphosphine oxide;Trimethylolpropane ethoxylate; Trimethylolpropane propoxylate;Triphenylphosphine oxide and mixtures thereof.
 45. The thermochromicsystem of claim 44, wherein the polymer comprises a poly(vinylacetal) ora poly(vinylacetal) copolymer.
 46. The thermochromic system of claim 45,wherein the polymer comprisespoly(vinylbutyral-co-vinylalcohol-co-vinylacetate).
 47. A thermochromicsystem which comprises a polymer layer which comprises: a) a transitionmetal ion; and b) a ligand capable of forming a HεMLC with thetransition metal ion; wherein the polymer is selected from the groupconsisting of poly(hydroxyethyl methacrylate); poly(1-glycerolmethacrylate); hydroxyalkylcelluloses; urethanes;poly(2-ethyl-2-oxazoline); poly(N-vinylpyrrolidone);poly(ethylene-co-vinylalcohol); poly(vinyl methyl ether);polyacrylamide; poly(N,N-dimethylacrylamide); polyvinylpyridines,copolymers thereof and mixtures thereof.
 48. The thermochromic system ofclaim 47 wherein the transition metal ion is selected from the groupconsisting of Fe(II), Co(II), Ni(II), Cu(II) and mixtures thereof. 49.The thermochromic system of claim 48 wherein the ligand is iodide. 50.The thermochromic system of claim 49 wherein the system comprises aphosphine compound with the following structure:

wherein R₁, R₂ and R₃ are independently selected from alkyl, cycloalkyl,substituted or unsubstituted aryl.
 51. The thermochromic system ofclaims 49 wherein the system as prepared comprises a phosphine compoundwith the following structure:

wherein R₁, R₂ and R₃ are independently selected from alkyl, cycloalkyl,substituted or unsubstituted aryl.